U.S. patent application number 10/341435 was filed with the patent office on 2004-01-22 for non-toxic corrosion-protection pigments based on manganese.
Invention is credited to Phelps, Andrew Wells, Sturgill, Jeffrey A..
Application Number | 20040011252 10/341435 |
Document ID | / |
Family ID | 30444023 |
Filed Date | 2004-01-22 |
United States Patent
Application |
20040011252 |
Kind Code |
A1 |
Sturgill, Jeffrey A. ; et
al. |
January 22, 2004 |
Non-toxic corrosion-protection pigments based on manganese
Abstract
Corrosion-inhibiting pigments based on manganese are described
that contain a trivalent or tetravalent manganese/valence
stabilizer complex. An inorganic or organic material is used to
stabilize the trivalent or tetravalent manganese ion to form a
compound that is sparingly soluble, exhibits low solubility, or is
insoluble in water, depending upon the intended usage. Specific
stabilizers are chosen to control the release rate of trivalent or
tetravalent manganese during exposure to water and to tailor the
compatibility of the powder when used as a pigment in a chosen
binder system. Stabilizers may also modify the processing and
handling characteristics of the formed powders. Manganese/valence
stabilizer combinations are chosen based on the well-founded
principles of manganese coordination chemistry. Many
manganese-valence stabilizer combinations are presented that can
equal the performance of conventional hexavalent chromium or
tetravalent lead systems. It is emphasized that this abstract is
provided to comply with the rules requiring an abstract which will
allow a searcher or other reader to quickly ascertain the subject
matter of the technical disclosure. It is submitted with the
understanding that it will not be used to interpret or limit the
scope or meaning of the claims.
Inventors: |
Sturgill, Jeffrey A.;
(Fairborn, OH) ; Phelps, Andrew Wells; (Kettering,
OH) |
Correspondence
Address: |
Killworth, Gottman,
Hagan & Schaeff, L.L.P.
One Dayton Centre, Suite 500
Dayton
OH
45402-2023
US
|
Family ID: |
30444023 |
Appl. No.: |
10/341435 |
Filed: |
January 13, 2003 |
Current U.S.
Class: |
106/401 ;
106/14.11; 106/14.12; 106/14.15; 106/14.22; 106/14.41; 106/14.42;
106/14.43; 106/14.44; 106/436; 106/450; 106/455; 106/479; 106/481;
106/499; 423/599; 427/299; 427/327 |
Current CPC
Class: |
C09C 1/34 20130101; C01P
2006/34 20130101; C01P 2006/40 20130101; C09C 1/00 20130101; C01G
45/1221 20130101; C09D 5/082 20130101 |
Class at
Publication: |
106/401 ;
423/599; 427/327; 427/299; 106/479; 106/481; 106/499; 106/455;
106/436; 106/450; 106/14.11; 106/14.15; 106/14.12; 106/14.22;
106/14.41; 106/14.42; 106/14.43; 106/14.44 |
International
Class: |
C01G 045/00 |
Claims
We claim:
1. A corrosion-inhibiting pigment comprising manganese, wherein the
manganese is trivalent manganese, tetravalent manganese, or
combinations thereof, and a valence stabilizer combined to form a
manganese/valence stabilizer complex.
2. The pigment of claim 1 wherein the manganese/valence stabilizer
complex has a solubility in water of between about 1.times.10.sup.0
and about 1.times.10.sup.-17 moles per liter of manganese at about
25.degree. C. and about 760 Torr.
3. The pigment of claim 2 wherein the solubility of the
manganese/valence stabilizer complex in water is between about
1.times.10.sup.-1 and about 1.times.10.sup.4 moles per liter of
manganese at about 25.degree. C. and about 760 Torr.
4. The pigment of claim 2 wherein the solubility of the
manganese/valence stabilizer complex in water is between about
1.times.10.sup.-6 and about 1.times.10.sup.-8 moles per liter of
manganese at about 25.degree. C. and about 760 Torr.
5. The pigment of claim 2 wherein the solubility of the
manganese/valence stabilizer complex in water is between about
1.times.10.sup.-9 and about 1.times.10.sup.-7 moles per liter of
manganese at about 25.degree. C. and about 760 Torr.
6. The pigment of claim 1 wherein there is an electrostatic barrier
layer around the manganese/valence stabilizer complex in aqueous
solution.
7. The pigment of claim 1 wherein the manganese/valence stabilizer
complex acts as an ion exchange agent towards corrosive ions.
8. The pigment of claim 1 wherein the manganese/valence stabilizer
complex decomposes above about 100.degree. C.
9. The pigment of claim 1 wherein the manganese/valence stabilizer
complex melts above about 50.degree. C.
10. The pigment of claim 1 wherein the valence stabilizer is an
inorganic valence stabilizer or an organic valence stabilizer.
11. The pigment of claim 10 wherein the valence stabilizer is the
inorganic valence stabilizer selected from molybdates, tungstates,
vanadates, niobates, tantalates, tellurates, periodates, iodates,
antimonates, stannates, sulfates, polyphosphates, titanates,
zirconates, oxygen, bismuthates, germinates, carbonates, arsenates,
phosphates, borates, aluminates, silicates, or combinations
thereof.
12. The pigment of claim 1 wherein the valence stabilizer is the
inorganic valence stabilizer selected from molybdates, tungstates,
vanadates, niobates, tantalates, tellurates, periodates, iodates,
oxygen, antimonates, stannates, sulfates, polyphosphates,
titanates, zirconates, phosphates, borates, aluminates, silicates,
or combinations thereof.
13. The pigment of claim 1 wherein the manganese/valence stabilizer
complex has a central cavity containing a manganese ion and an
additional ion.
14. The pigment of claim 13 wherein the additional ion is B.sup.+3,
Al.sup.+3, Si.sup.+4, P.sup.+5, Ti.sup.+4, V.sup.+5, V.sup.+4,
Cr.sup.+6, Cr.sup.+3, Mn.sup.+2, Fe.sup.+3, Fe.sup.+2, Co.sup.+2,
Co.sup.+3, Ni.sup.+2, Ni.sup.+3, Ni.sup.+4, Cu.sup.+2, Cu.sup.+3,
Zn.sup.+2, Ga.sup.+3, Ge.sup.+4, As.sup.+5, As.sup.+3, Zr.sup.+4,
or Ce.sup.+4.
15. The pigment of claim 10 wherein the valence stabilizer is the
organic valence stabilizer selected from monoamines; diamines;
triamines; tetraamines; pentamines; hexamines; five- or
six-membered heterocyclic rings containing one to four nitrogen
atoms optionally having additional nitrogen, sulfur, or oxygen
binding sites; five- or six-membered heterocyclic rings containing
one or two sulfur atoms and having additional nitrogen binding
sites; five- or six-membered heterocyclic rings containing one or
two oxygen atoms and having additional nitrogen binding sites;
(two-, three-, four-, six-, eight-, or ten-)membered nitrogen,
nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic
oligothioketones or dithiolenes; diazenes; thio-, amido-, or
imido-derivatives of hypophosphoric, phosphoric, or diphosphoric
acids and salts; thio-derivatives of hypophosphoric, phosphoric, or
diphosphoric acids and salts; azo compounds, triazenes, formazans,
azines, hydrazones, or Schiff Bases containing at least two azo,
imine, or azine groups; azo compounds, triazenes, formazans,
azines, hydrazones, or Schiff Bases; ortho- (for aryl) or alpha- or
beta- (for alkyl) substituted azo compounds, triazenes, formazans,
azines, hydrazones, or Schiff Bases; oximes; amidines and imido
compounds; dithio ligands; amides; amino acids; N-(thio)acyl
7-aminobenzylidenimines; (thio)hydroxamates; alpha- or
ortho-aminothio(di)carboxylic acids and salts;
(thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones;
silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl
imines; (thio)aryl amines and imines; guanylureas; guanidinoureas;
2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines;
1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides;
2-acylthioacetamides; dithiodicarbonic diamides;
trithiodicarboxylic acids and salts; monothiocarbamates;
monothioethers; dithioethers; trithioethers; tetrathioethers;
pentathioethers; hexathioethers; disulfides; monophosphines;
diphosphines; triphosphines; tetraphosphines; pentaphosphines;
hexaphosphines; five- or six-membered heterocyclic rings containing
one or two sulfur atoms optionally having additional sulfur,
oxygen, or phosphorus binding sites; five- or six-membered
heterocyclic rings containing one to three phosphorus atoms
optionally having additional phosphorus, nitrogen, oxygen, or
sulfur binding sites; five- or six-membered heterocyclic rings
containing one to four nitrogen atoms and having additional
phosphorus binding sites; five- or six-membered heterocyclic rings
containing one or two oxygen atoms and optionally having additional
sulfur or phosphorus binding sites; (five-, seven-, or
nine-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen
macrocyclics; (two- to ten-)membered sulfur, sulfur-oxygen, or
sulfur-phosphorus macrocyclics, not including oligothioketones or
dithiolenes; (two- to ten-)membered phosphorus,
nitrogen-phosphorus, or oxygen-phosphorus macrocyclics; (two- to
ten-)membered oxygen macrocyclics; thio-, amido-, or
imido-derivatives of phosphonic and diphosphonic acids and salts
containing no sulfur binding sites; amido-, or imido-derivatives of
hypophosphoric, phosphoric, or diphosphoric acids and salts
containing no sulfur binding sites; dithioperoxydiphosphoramide- s;
dithioperoxydiphosphoric acids and salts;
monothioperoxydiphosphoramide- s; monothioperoxydiphosphoric acids
and salts; monothiophosphoric acids; phosphoro(dithioperoxoic)
acids and salts; azo compounds, triazenes, formazans, azines, or
Schiff Bases; silylamines; silazanes; guanidines and diguanidines;
pyridinaldimines; hydrazones; hydramides; nitriles; thioureas and
thioamides; ureas and pseudoureas; biurets; monothio ligands;
diketone ligands; dithioperoxydicarbonic acids and salts;
dithioacyl disulfides; tetrathioperoxydicarbonic diamides; (hexa-,
penta-, or tetra-)thioperoxydicarbonic acids and salts;
1,2-dithiolates; rhodanines; dithiocarbimates; (thio)xanthates;
S-(alkyl- or aryl-thio)thiocarboxylic acids and salts;
phosphinodithioformates; (thio)borates and (thio)boronates;
(thio)arsonic acids and salts; (thio)antimonic acids and salts;
phosphine and arsine sulfides or oxides; beta-hydroxyketones and
aldehydes; squaric acids and salts; carbonates; carbamates and
carbimates; carbazates; imidosulfurous diamides; sulfurdiimines;
thiocarbonyl and mercapto oximes; 2-nitrothiophenols;
2-nitrilo(thio)phenols; acylcyanamides; imidates;
2-amidinoacetates; beta-ketoamines; 3-aminoacrylamides and
3,3-diaminoacrylamides; 3-aminoacrylic acids and salts and
3-hydroxy-3-aminoacrylic acids and salts; 2-nitroanilines; amine
and diazine N-oxides; hydrazides and semicarbazides; (amino- or
imino-)aryl phosphines; (thio- or hydroxy-)aryl phosphines;
arsines; five- or six-membered heterocyclic rings containing one
arsenic atom optionally having additional arsenic binding
sites;(two- to six-)membered arsenic macrocyclics; selenoethers;
five- or six-membered heterocyclic rings containing one or two
selenium atoms optionally having additional selenium binding sites;
(two- to six-)membered selenium macrocyclics; 1,3-diselenoketones;
1,1-diselenolates; diselenocarbamates; selenophosphoric acids and
salts; selenocarbonates; cyanide, isocyanide, and cyanamide
ligands; nitrosyl and nitrite ligands; azide ligands; thiolates and
selenolates; (thio)cyanate ligands; diene or bicyclic or tricyclic
hydrocarbon ligands; carbonyl, halogen, oxo, and hydroxo ligands;
or combinations thereof.
16. The pigment of claim 15 wherein the organic valence stabilizer
is selected from monoamines; diamines; triamines; tetraamines;
pentamines; hexamines; five- or six-membered heterocyclic rings
containing one to four nitrogen atoms optionally having additional
nitrogen, sulfur, or oxygen binding sites; five- or six-membered
heterocyclic rings containing one or two sulfur atoms and having
additional nitrogen binding sites; five- or six-membered
heterocyclic rings containing one or two oxygen atoms and having
additional nitrogen binding sites; (two-, three-, four-, six-,
eight-, or ten-)membered nitrogen, nitrogen-sulfur, or
nitrogen-oxygen macrocyclics; macrocyclic oligothioketones or
dithiolenes; diazenes; thio-, amido-, or imido-derivatives of
hypophosphoric, phosphoric, or diphosphoric acids and salts; azo
compounds, triazenes, formazans, azines, hydrazones, or Schiff
Bases containing at least two azo, imine, or azine groups; azo
compounds, triazenes, formazans, azines, hydrazones, or Schiff
Bases; ortho- (for aryl) or alpha- or beta- (for alkyl) substituted
azo compounds, triazenes, formazans, azines, hydrazones, or Schiff
Bases; oximes; amidines and imido compounds; dithio ligands;
amides; amino acids; N-(thio)acyl 7-aminobenzylidenimines;
(thio)hydroxamates; alpha- or ortho-aminothio(di)carboxylic acids
and salts; (thio)semicarbazones; (thio)acyl hydrazones;
(thio)carbazones; silylaminoalcohols; thioalkyl amines and imines;
hydroxyalkyl imines; (thio)aryl amines and imines; guanylureas;
guanidinoureas; biurets; diketone ligands; amido- or
imido-derivatives of hypophosphoric, phosphoric, or diphosphoric
acids and salts; beta-hydroxyketones and -aldehydes; squaric acids
and salts; carbamates and carbimates; 2-nitrosophenols;
2-nitrophenols; N-nitrosohydroxylamines; 1,3-monothioketones;
monothiomalonamides; 2-thioacylacetamides; 2-acylthioacetamides;
dithiodicarbonic diamides; trithiodicarboxylic acids and salts;
monothiocarbamates; (thio)cyanate ligands; oxo and hydroxo ligands;
or combinations thereof.
17. The pigment of claim 15 wherein the organic valence stabilizer
is the diazene selected from diazeneformimidamides,
diazeneformamides, diazenefonmothioamides, diazeneacetimidamides,
diazeneacetothioamides, diazeneformimidic acids and salts,
diazeneacetimidic acids and salts, diazenecarbothioic acids and
salts, diazenecarbodithioic acids and salts, diazeneformimidothioic
acids and salts, diazeneformaldehydes, diazeneformothioaldehydes,
diazeneacetaldehydes, diazeneacetothioaldehyde- s,
diazenediformamides, diazenediformothioamides, diazenediacetamides,
diazenediacetothioamides, diazeneacetimidothioic acids and salts,
imidoyldiazenes, diazenediformimidamides, diazenediacetimidamides,
diazenediformimidic acids and salts, diazenediacetimidic acids and
salts, diazenediformimidothioic acids and salts,
diazenediacetimidothioic acids and salts, diazenedicarbothioic
acids, diazenedicarbodithioic acids, diazeneformic acids,
diazenediformic acids, diazeneacetic acids, diazenediacetic acids,
diazenediformaldehydes, diazenediformothioaldehyde- s,
diazenediacetaldehydes, diazenediacetothioaldehydes,
diimidoyldiazenes, or combinations thereof.
18. The pigment of claim 15 wherein the organic valence stabilizer
is the thio-, amido-, or imido-derivative of hypophosphoric,
phosphoric, or diphosphoric acids and salts selected from
phosphoramidimidic triamides, phosphoramidimidic acids and salts,
phosphorodiamidimidic acids and salts, phosphorodiamidimidothioic
acids and salts, phosphoramidimidothioic acids and salts,
phosphorodiamidimidodithioic acids and salts,
phosphoramidimidodithioic acids and salts, (di- or
mono-)thiohypophospboric acids and salts, (di- or
mono-)thiohypophosphora- mides, phosphoramidic acids and salts,
phosphorimidic acids and salts, (di- or mono-)thioimidodiphosphoric
acids and salts, (di- or mono-)thiohydrazidodipbosphoric acids and
salts, (di- or mono-)thioimidodiphosphoramides, (di- or
mono-)thiohydrazidodiphosphorami- des, phosphoric triamides, (di-
or mono-)thiodiphosphoramides, (di- or mono-)thiodiphosphoric acids
and salts, (tetra-, tri-, di-)thiophosphoric acids and salts,
phosphoro(dithioperoxo)(mono-,di-, or tri-)thioic acids and salts,
phosphorimido(mono-, di-, or tri-)thioic acids and salts,
phosphorothioic triamides, phosphoramido(mono, di- or tri-)thioic
acids and salts, phosphorodiamido(mono, di- or tri-)thioic acids
and salts, or combinations thereof.
19. The pigment of claim 15 wherein the organic valence stabilizer
is a substituent for the ortho- (for aryl) or alpha- or beta- (for
alkyl) substituted azo compounds, triazenes, formazans, azines,
hydrazones, or Schiff Bases selected from amino, imino, oximo,
diazeno, hydrazido, thiol, mercapto, thiocarbonyl, hydroxy, carbox,
and carbonyl substituents, or combinations thereof.
20. The pigment of claim 15 wherein the organic valence stabilizer
is the oxime selected from monooximes, dioximes, carbonyl oximes,
imine oximes, hydroxy oximes, amino oximes, amido oximes, hydrazone
oximes, azo oximes, or combinations thereof.
21. The pigment of claim 15 wherein the organic valence stabilizer
is the amidine and imido compound selected from amidines,
diamidines, biguamides, biguanidines, diamidinomethanes,
imidoylguanidines, amidinoguanidines, diformamidine oxides,
sulfides, and disulfides, imidodicarbonimidic acids and salts,
diimidodicarbonimidic acids and salts, thioimidodicarbonimidic
acids and salts, thiodiimidodicarbonimidic acids and salts,
diimidoylimines, diimidoylhydrazides, imidosulfamides,
diimidosulfamides, O-amidinocarbamates, O- or S-amidino(mono-, di-,
or peroxy-)thiocarbamates, N-hydroxy(or N,N'-dihydroxy)amidines,
diimidosulfuric acids and salts, or combinations thereof.
22. The pigment of claim 15 wherein the organic valence stabilizer
is the dithio ligand selected from dithioimidodialdehydes,
dithiohydrazidodialdehydes, dithioimidodicarbonic acids and salts,
dithiohydrazidodicarbonic acids and salts, 1,3-dithioketones,
1,2-dithioketones, dithiomalonamides, 2-thioacylthioacetamides,
dithioacyl sulfides, trithiodicarbonic diamides, (penta-, tetra-,
tri-)thiodicarbonic acids and salts, beta-mercaptothioketones and
-aldehydes, N-(aminomethylthiol)thioureas, dithiooxamides,
1,1-dithiolates, (di- or per-)thiomonocarboxylic acids and salts,
(tetra- or per-)thiodicarboxylic acids and salts, (di-, tri-, or
per-)thiocarbonates, dithiocarbamates (including
N-hydroxydithiocarbamate- s and N-mercaptodithiocarbamates),
dithiocarbazates, or combinations thereof.
23. The pigment of claim 15 wherein the organic valence stabilizer
is the amide selected from monoamides, lactams, amidinoamides,
guanidinoamides, imidoylamides, polyamides, polylactams, or
combinations thereof.
24. The pigment of claim 15 wherein the organic valence stabilizer
is the thio-, amido-, or imido-derivative of phosphonic and
diphosphonic acids and salts selected from phosphonitrile amides,
phosphonimidic diamides, phosphonamidimidic acids and salts,
phosphonamidimidothioic acids and salts, dithioimidodiphosphonic
acids and salts, dithiohydrazidodiphosphon- ic acids and salts,
dithioimidodiphosphonamides, dithiohydrazidodiphosphon- amides,
dithiodiphosphonamides, dithiodiphosphonic acids and salts,
dithioperoxydiphosphonamides, dithioperoxydiphosphonic acids and
salts, (di- and tri-)thiophosphonic acids and salts,
phosphono(dithioperoxo)thio- ic acids and salts,
phosphono(dithioperoxo)dithioic acids and salts,
phosphonimidothioic acids and salts, phosphonimidodithioic acids
and salts, phosphonothioic acids and salts, phosphonanidothioic
acids and salts, phosphonamidimidodithioic acids and salts,
monothioimidodiphosphon- ic acids and salts,
monothiohydrazidodiphosphonic acids and salts,
monothioimidodiphosphonamides, monothiohydrazidodiphosphonamides,
monothiodiphosphonamides, monothiodiphosphonic acids and salts,
monothioperoxydiphosphonamides, monothioperoxydiphosphonic acids
and salts, monothiophosphonic acids and salts,
phosphono(dithioperoxoic) acids and salts, or combinations
thereof.
25. The pigment of claim 15 wherein the organic valence stabilizer
is the amido- or imido-derivative of hypophosphoric, phosphoric, or
diphosphoric acids and salts containing no sulfur binding sites
selected from hypophosphoric acids and salts, hypophosphoramides,
imidodiphosphoric acids and salts, hydrazidodiphosphoric acids and
salts, imidodiphosphoramides, hydrazidodiphosphoramides,
diphosphoramides, or combinations thereof.
26. The pigment of claim 15 wherein the organic valence stabilizer
is the amido- or imido-derivative of phosphonic or diphosphonic
acids and salts containing no sulfur binding sites selected from
imidodiphosphonic acids and salts, hydrazidodiphosphonic acids and
salts, imidodiphosphonamides, hydrazidodiphosphonamides,
diphosphonamides, phosphonimidic acids and salts, phosphonamidic
acids and salts, phosphonic diamides, or combinations thereof.
27. The pigment of claim 15 wherein the organic valence stabilizer
is the thiourea and thioamide selected from thioureas,
thiocarboxamides, thioacylthioureas, acylthioureas, thioacylureas,
thioaroylthioureas, aroylthioureas, thioaroylureas, thioimidates,
thioguanylureas, guanidinothioureas, amidinothioamides,
guanidinothioamides, imidoylthioamides, 3-aminothioacrylamides,
thiohydrazides, thiosemicarbazides, (mono- and di-)thiobiurets,
(mono- and di-)thioisobiurets, (mono- and di-)thiobiureas,
N-(aminomethylol)thiourea- s, N-(aminomethylthiol)ureas,
beta-mercaptocarboxamides, or combinations thereof.
28. The pigment of claim 15 wherein the organic valence stabilizer
is the biuret selected from biurets, triurets, isobiurets, biureas,
triureas, acylureas, aroylureas, N-(aminomethylol)ureas, or
combinations thereof.
29. The pigment of claim 15 wherein the organic valence stabilizer
is the monothio ligand selected from beta-aminothiones,
3-aminothioacrylic acids and salts, 3-mercapto-3-aminothioacrylic
acids and salts, N-thioacyl benzylidenimines, thioimidodialdehydes,
thiohydrazidodialdehydes, thioimidodicarbonic acids and salts,
thiohydrazidodicarbonic acids and salts, 1,2-monothioketones,
trithioperoxydicarbonic diamides, dithioperoxydicarbonic diamides,
dithiodicarbonic acids and salts, trithioperoxydicarbonic acids and
salts, beta-hydroxythioketones, beta-hydroxythioaldehydes,
beta-mercaptoketones, beta-mercaptoaldehydes, monothiooxamides,
beta-mercaptocarboxylic acids and salts,
beta-mercaptothiocarboxylic acids and salts,
beta-hydroxythiocarboxylic acids and salts, S-alkylthiocarboxylic
acids and salts, S-arylthiocarboxylic acids and salts,
S-alkyldisulfidocarboxylic acids and salts,
S-aryldisulfidocarboxylic acids and salts, monothiomonocarboxylic
acids and salts, dithiodicarboxylic acids and salts,
monothiocarbonates, monothiocarbazates, monothiocarbimates,
mercaptoalcohols, silylmercaptoalcohols, or combinations
thereof.
30. The pigment of claim 15 wherein the organic valence stabilizer
is the diketone ligand selected from imidodialdehydes,
hydrazidodialdehydes, imidodicarbonic acids and salts,
hydrazidodicarbonic acids and salts, imidodisulfamic acids and
salts, imidodisulfuric acids and salts, 1,3-diketones,
1,3,5-triketones, 1,2-diketones, 1,2,3-triketones, tropolonates,
ortho-quinones, malonamides, 2-acylacetamides, monothiodicarbonic
diamides, monothiodicarbonic acids and salts, trithionic acids and
salts, oxamides, dicarboxylic acids, or combinations thereof.
31. The pigment of claim 15 wherein the organic valence stabilizer
is the S-(alkyl- or aryl-thio)thiocarboxylic acid and salt selected
from S-(alkylthio)thiocarboxylic acids and salts,
S-(arylthio)thiocarboxylic acids and salts,
S,S-thiobisthiocarboxylic acids and salts,
S-(alkyldisulfido)thiocarboxylic acids and salts,
S-(aryldisulfido)thioca- rboxylic acids and salts,
S,S'-disulfidobisthiocarboxylic acids and salts, or combinations
thereof.
32. The pigment of claim 15 wherein the organic valence stabilizer
is the phosphine and arsine sulfide or oxide selected from
phosphine P-sulfides, aminophosphine sulfides, arsine As-sulfides,
aminoarsine sulfides, phosphine P-oxides, aminophosphine oxides,
arsine As-oxides, aminoarsine oxides, or combinations thereof.
33. The pigment of claim 15 wherein a solubility in water of the
manganese/valence stabilizer complex is adjusted by an addition of
a substituent group on the organic valence stabilizer.
34. The pigment of claim 33 wherein the solubility in water is
increased by the addition of the substituent group selected from
sulfonate groups (--SO.sub.3.sup.-), carboxyl groups
(--CO.sub.2--), hydroxyl groups (--OH), ester groups
(--CO.sub.3--), carbonyl groups (.dbd.C.dbd.O), amine groups
(--NH.sub.2), nitrosamine groups (.dbd.N--N.dbd.O), carbonylnitrene
groups (--CO--N), sulfoxide groups (.dbd.S.dbd.O), sulfone groups
(.dbd.S[.dbd.O].sub.2), sulfinyl groups (--N.dbd.S.dbd.O),
sulfodiimines (.dbd.S[=NH].sub.2), sulfonyl halide groups
(--S[.dbd.O].sub.2X), sulfonamide groups
(--S[.dbd.O].sub.2NH.sub.2), monohalosulfonamide groups
(--S[.dbd.O].sub.2NHX), dihalosulfonamide groups
(--S[.dbd.O].sub.2MX.sub.2), halosulfonate groups
(--S[.dbd.O].sub.2OX), halosulfonate amide groups
(.dbd.N--S[.dbd.O].sub.- 2X), aminosulfonate groups
(.dbd.N--S[.dbd.O].sub.2OH), iminosulfonate groups
(--N[SO.sub.3.sup.-].sub.1-2), phosphonate groups
(PO.sub.3.sup.-2), phosphonamide groups (--PO.sub.2NH.sub.2.sup.-),
phosphondiamide groups (--PO[NH.sub.2].sub.2), aminophosphonate
groups (.dbd.N--PO.sub.3.sup.-2), iminophosphonate groups
(--N[PO.sub.3.sup.-2].sub.1-2), or combinations thereof.
35. The pigment of claim 33 wherein the solubility in water is
decreased by the addition of the substituent group selected from
nitro groups (--NO.sub.2), perfluoroalkyl groups
(--C.sub.xF.sub.2x+1), perchloroalkyl groups
(--C.sub.xCl.sub.2x+1), nitramine groups (.dbd.N--NO.sub.2),
thioketone groups (.dbd.C.dbd.S), sulfenyl halide groups (--S--X),
sulfur dihaloimide groups (--N.dbd.SX.sub.2), or combinations
thereof.
36. The pigment of claim 15 wherein an electrostatic barrier layer
of the manganese/valence stabilizer complex is adjusted by an
addition of a substituent group on the organic valence
stabilizer.
37. The pigment of claim 36 wherein the electrostatic barrier layer
is increased by the addition of the substituent group selected from
ketones (.dbd.C.dbd.O), thioketones (.dbd.C.dbd.S), amides
(--C[.dbd.O]NR.sub.2), thioamides (--C[.dbd.S]--NR.sub.2), nitriles
or cyano groups (--CN), isocyanides (--NC), nitroso groups
(--N.dbd.O), thionitroso groups (--N.dbd.S), nitro groups
(--NO.sub.2), azido groups (--N.sub.3), cyanamide or cyanonitrene
groups (.dbd.N--CN), cyanate groups (--O--CN), isocyanate groups
(--N.dbd.C.dbd.O), thiocyanate groups (--S--CN), isothiocyanate
groups (--N.dbd.C.dbd.S), nitrosamine groups (.dbd.N--N.dbd.O),
thionitrosamine groups (.dbd.N--N.dbd.S), nitramine groups
(.dbd.N--NO.sub.2), thionitramine groups (.dbd.N--NS.sub.2),
carbonylnitrene groups (--CO--N), thiocarbonylnitrene groups
(--CS--N), sulfenyl halides (--S--X), sulfoxides (.dbd.S.dbd.O),
sulfones (.dbd.S[.dbd.O].sub.2), sulfinyl groups (--N.dbd.S.dbd.O),
thiosulfinyl groups (--N.dbd.S=S), sulfenyl thiocyanato groups
(--S--S--CN), sulfenyl cyanato groups (--S--O--CN), sulfodiimine
groups (.dbd.S[=NH].sub.2), sulfur dihaloimido groups
(--N.dbd.SX.sub.2), sulfur oxide dihaloimido groups
(--N.dbd.S[.dbd.O]X.sub.2), aminosulfur oxide trihalide groups
(.dbd.N--S[.dbd.O]X.sub.3), sulfonyl azide groups
(--S[.dbd.O].sub.2N.sub- .3), sulfonyl thiocyanate groups
(--S[.dbd.O].sub.2SCN), sulfonyl cyanate groups
(--S[.dbd.O].sub.2OCN), sulfonyl cyanide groups
(--S[.dbd.O].sub.2CN), halosulfonate groups (--S[.dbd.O].sub.2OX),
phosphonyl thiocyanate groups (--P[.dbd.O]OHSCN), phosphonyl
cyanate groups (--P[.dbd.O]OHOCN), phosphonyl cyanide groups
(--P[.dbd.O]OHCN), or combinations thereof.
38. The pigment of claim 1 further comprising a solubility control
agent.
39. The pigment of claim 38 wherein the solubility control agent is
a cationic solubility control agent or an anionic solubility
control agent.
40. The pigment of claim 39 wherein the solubility control agent is
the cationic solubility control agent selected from H.sup.+;
Li.sup.+; Na.sup.+; K.sup.+; Rb.sup.+; Cs.sup.+; NH.sub.4.sup.+;
Mg.sup.+2; Ca.sup.+2; Sr.sup.+2; Be.sup.+2; Ba.sup.+2; Y.sup.+3;
La.sup.+3; Ce.sup.+3; Ce.sup.+4; Nd.sup.+3; Pr.sup.+3; Sc.sup.+3;
Sm.sup.+3; Eu.sup.+3; Eu.sup.+2; Gd.sup.+3; Tb.sup.+3; Dy.sup.+3;
Ho.sup.+3; Er.sup.+3; Tm.sup.+3; Yb.sup.+3; Lu.sup.+3; Ti.sup.+4;
Zr.sup.+4; Ti.sup.+3; Hf.sup.+4; Nb.sup.+5; Ta.sup.+5; Nb.sup.+4;
Ta.sup.+4; V.sup.+5; V.sup.+4; V.sup.+3; Mo.sup.+6; W.sup.+6;
Mo.sup.+5; W.sup.+5; Mo.sup.+4; W.sup.+4; Cr.sup.+3; Mn.sup.+2;
Mn.sup.+3; Mn.sup.+4; Fe.sup.+2; Fe.sup.+3; Co.sup.+2; Co.sup.+3;
Ni.sup.+2; Ni.sup.+3; Ni.sup.+4; Ru.sup.+2; Ru.sup.+3; Ru.sup.+4;
Ru.sup.+3; Ir.sup.+3; Rh.sup.+2; Ir.sup.+2; Pd.sup.+4; Pt.sup.+4;
Pd.sup.+2; Pt.sup.+2; Os.sup.+4; Cu.sup.+; Cu.sup.+2; Cu.sup.+3:
Ag.sup.+; Ag.sup.+2; Ag.sup.+3; Au.sup.+; Au.sup.+2; Au.sup.+3;
Zn.sup.+2; Cd.sup.+2; Hg.sup.+; Hg.sup.+2; Al.sup.+3; Ga.sup.+3;
Ga.sup.+; In.sup.+3; In.sup.+; Tl.sup.+3; Tl.sup.+; Ge.sup.+4;
Ge.sup.+2; Sn.sup.+4; Sn.sup.+2; Pb.sup.+4; P.sup.+2; Sb.sup.+3;
Sb.sup.+5; As.sup.+3; As.sup.+5; Bi.sup.+3; Bi.sup.+5; organic
compounds containing at least one N.sup.+ site; organic compounds
containing at least one phosphonium site; organic compounds
containing at least one arsonium site; organic compounds containing
at least one stibonium site; organic compounds containing at least
one oxonium site; organic compounds containing at least one
sulfonium site; organic compounds containing at least one
selenonium site; organic compounds containing at least one iodonium
site; quaternary ammonium compounds having a formula
NR.sub.4.sup.+, where R is an alkyl, aromatic, or acyclic organic
constituent; or combinations thereof.
41. The pigment of claim 40 wherein the cationic solubility control
agent is selected from H.sup.+; Li.sup.+; Na.sup.+; K.sup.+;
Rb.sup.+; Cs.sup.+; NH.sub.4.sup.+; Mg.sup.+2; Ca.sup.+2;
Sr.sup.+2; Y.sup.+3; La.sup.+3; Ce.sup.+3; Ce.sup.+4; Nd.sup.+3;
Pr.sup.+3; Sc.sup.+3; Sm.sup.+3; Eu.sup.+3; Eu.sup.+2; Gd.sup.+3;
Tb.sup.+3; Dy.sup.+3; Ho.sup.+3; Er.sup.+3; Tm.sup.+3; Yb.sup.+3;
Lu.sup.+3; Ti.sup.+4; Zr.sup.+4; Ti.sup.+3; Zr.sup.+4; Ti.sup.+3;
Hf.sup.+4; Nb.sup.+5; Ta.sup.+5; Nb.sup.+4, Ta.sup.+4; Mo.sup.+6;
W.sup.+6; Mo.sup.+5; W.sup.+5; Mo.sup.+4; W.sup.+4; Mn.sup.+2;
Mn.sup.+3; Mn.sup.+4 Fe.sup.+2; F.sup.+3; Co.sup.+2; Co.sup.+3;
Ru.sup.+2; Ru.sup.+3; Ru.sup.+4; Rh.sup.+3; Ir.sup.+3; Rh.sup.+2;
Ir.sup.+2; Pd.sup.+4; Pt.sup.+4; Pd.sup.+2; Pt.sup.+2; Cu.sup.+;
Cu.sup.+2; Cu.sup.+3; Ag.sup.+; Ag.sup.+2; Ag.sup.+3; Au.sup.+;
Au.sup.+3; Au.sup.+3+; Zn.sup.'2; Al.sup.+3; Ga.sup.+3; Ga.sup.+;
In.sup.+3; In.sup.+; Ge.sup.+4; Ge.sup.+2; Sn.sup.+4; Sn.sup.+2;
Sb.sup.+3; Sb.sup.+5; Bi.sup.+3; Bi.sup.+5; organic compounds
containing at least one N.sup.+ site; organic compounds containing
at least one phosphonium site; organic compounds containing at
least one stibonium site; organic compounds containing at least one
oxonium site; organic compounds containing at least one sulfonium
site; organic compounds containing at least one iodonium site;
quaternary ammonium compounds having a formula NR.sub.4.sup.+,
where R is an alkyl, aromatic, or acyclic organic constituent; or
combinations thereof.
42. The pigment of claim 39 wherein the solubility control agent is
the anionic solubility control agent selected from fluorotitanates,
chlorotitanates, fluorozirconates, chlorozirconates,
fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates,
molybdates, tungstates, permanganates, fluoroinanganates,
chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates,
chlorocobaltates, fluorozincates, chlorozincates, borates,
fluoroborates, fluoroaluminates, chloroaluminates, carbonates,
silicates, fluorosilicates, fluorostannates, nitrates, nitrites,
azides, cyanamides, phosphates, phosphites, phosphonates,
phosphinites, thiophosphates, thiophosphites, thiophosphonates,
thiophosphinites, fluorophosphates, fluoroantimonates,
chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates,
dithionites, dithionates, fluorosulfates, tellurates, fluorides,
chlorides, chlorates, perchlorates, bromides, bromates, iodides,
iodates, periodates, heteropolyanions, ferricyanides,
ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates,
cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates,
cyanatomanganates, thiocyanates, thiocyanatoferrates,
thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates,
cyanamides, cyanamidoferrates, cyanamidocobaltates,
cyanamidocuprates, cyanamidomanganates, nitritoferrates,
nitritocobaltates, azides, (thio)carboxylates,
di(thio)carboxylates, tri(thio)carboxylates,
tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates,
tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates,
di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides,
di(thio)phosphonamides, tri(thio)phosphonamides,
amino(thio)phosphonates, diamino(thio)phosphonates,
triamino(thio)phosphonates, imino(thio)phosphonates,
diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates,
tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides,
tri(thio)sulfonamides, amino(thio)sulfonates,
diamino(thio)sulfonates, triamino(thio)sulfonates,
imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates,
di(thio)borates, (thio)boronates, organic silicates, stibonates,
cyanides, cyanochromates, cyanonickelates, cyanatochromates,
cyanatonickelates, thiocyanatochromates, thiocyanatonickelates,
cyanamidochromates, cyanamidonickelates, nitritonickelates,
arsonates, diarsonates, triarsonates, organic selenates,
diselenates, triselenates, arsenates, arsenites, fluoroarsenates,
chloroarsenates, selenates, selenites, fluorothallates,
chlorothallates, iodomercury anions, chloromercurates,
bromomercurates, osmates, fluoronickelates, chromates, Reinecke's
salt, vanadates, or combinations thereof.
43. The pigment of claim 42 wherein the anionic solubility control
agent is selected from fluorotitanates, chlorotitanates,
fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates,
fluorotantalates, chlorotantalates, molybdates, tungstates,
permanganates, fluoromanganates, chloromanganates, fluoroferrates,
chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates,
chlorozincates, borates, fluoroborates, fluoroaluminates,
chloroaluminates, carbonates, silicates, fluorosilicates,
fluorostannates, nitrates, nitrites, azides, cyanamides,
phosphates, phosphites, phosphonates, phosphinites, thiophosphates,
thiophosphites, thiophosphonates, thiophosphinites,
fluorophosphates, fluoroantimonates, chloroantimonates, sulfates,
sulfites, sulfonates, thiosulfates, dithionites, dithionates,
fluorosulfates, tellurates, fluorides, chlorides, chlorates,
perchlorates, bromides, bromates, iodides, iodates, periodates,
heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates,
cyanocuprates, cyanomanganates, cyanates, cyanatoferrates,
cyanatocobaltates, cyanatocuprates, cyanatomanganates,
thiocyanates, thiocyanatoferrates, thiocyanatocobaltates,
thiocyanatocuprates, thiocyanatomanganates, cyanamides,
cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates,
cyanamidomanganates, nitritoferrates, nitritocobaltates, azides,
(thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates,
tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates,
tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates,
di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides,
di(thio)phosphonamides, tri(thio)phosphonamides,
amino(thio)phosphonates, diamino(thio)phosphonat- es,
triamino(thio)phosphonates, imino(thio)phosphonates,
diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates,
tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides,
tri(thio)sulfonamides, amino(thio)sulfonates,
diamino(thio)sulfonates, triamino(thio)sulfonates,
imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates,
di(thio)borates, (thio)boronates, organic silicates, stibonates, or
combinations thereof.
44. The pigment of claim 1 wherein the manganese/valence stabilizer
complex is adsorbed or mixed onto, into, or with an inert medium
selected from oxides, hydroxides, phosphates, borates, silicates,
carbonates, aluminates, titanates, molybdates, tungstates,
oxalates, polymers, or combinations thereof.
45. The pigment of claim 1 wherein the pigment is colored.
46. The pigment of claim 1 wherein the pigment exhibits a color
change between manganese oxidation states.
47. The pigment of claim 1 wherein the pigment is light-fast.
48. A method of making a corrosion-inhibiting pigment comprising:
providing a solvent; providing a manganese source in the solvent
forming a manganese solution; providing a valence stabilizer; and
combining the manganese source and the valence stabilizer to form a
manganese/valence stabilizer complex.
49. The method of claim 48 wherein the manganese source is selected
from divalent manganese sources, trivalent manganese sources,
tetravalent manganese sources, heptavalent manganese sources, or
combinations thereof.
50. The method of claim 48 further comprising oxidizing the
manganese source.
51. The method of claim 50 wherein the manganese source is oxidized
by adding an oxidizer to the manganese solution.
52. The method of claim 51 wherein the oxidizer is a dissolved
solid, a liquid, or a gas.
53. The method of claim 51 wherein the oxidizer is selected from
peroxides, superoxides, persulfates, perborates, pernitrates,
perphosphates, percarbonates, persilicates, peraluminates,
pertitanates, perzirconates, permolybdates, pertungstates,
pervanadates, organic peroxyacid derivatives, ozone, hypochlorites,
chlorates, perchlorates, nitrates, nitrites, vanadates, iodates,
hypobromites, chlorites, bromates, permanganates, periodates,
dissolved oxygen, dissolved chlorine, dissolved fluorine, or
combinations thereof.
54. The method of claim 50 wherein the manganese source is oxidized
by electrolysis.
55. The method of claim 48 wherein the manganese/valence stabilizer
complex is formed by a process selected from precipitation,
evaporation, salting out with chemicals, freezing, freeze drying,
or firing at an elevated temperature.
56. The method of claim 55 wherein the manganese/valence stabilizer
complex is formed by precipitation.
57. The method of claim 48 wherein the manganese source is selected
from manganese oxide, manganese dioxide, manganomanganic oxide,
manganese sesquioxide, manganese hydroxide, manganese carbonate,
manganese silicate, manganese borate, manganese sulfide, manganese
phosphate, lithiated manganese spinel, manganese oxalate, manganese
nitrate, manganese sulfate, manganese perchlorate, manganese
chloride, manganese fluoride, manganese bromide, manganese iodide,
manganese bromate, manganese chlorate, manganese fluosilicate,
manganese fluotitanate, manganese fluozirconate, manganese
fluoborate, manganese fluoaluminate, manganese formate, manganese
acetate, manganese propionate, manganese butyrate, manganese
valerate, manganese benzoate, manganese glycolate, manganese
lactate, manganese tartronate, manganese malate, manganese
tartrate, manganese citrate, manganese benzenesulfonate, manganese
thiocyanate, manganese acetylacetonate, potassium permanganate,
sodium permanganate, lithium permanganate, ammonium permanganate,
magnesium permanganate, calcium permanganate, strontium
permanganate, barium permanganate, zinc permanganate, ferric
permanganate, nickel permanganate, copper permanganate, cobalt
permanganate, cerium permanganate, lanthanum permanganate, yttrium
permanganate, aluminum permanganate, or combinations thereof.
58. The method of claim 48 wherein the solvent comprises water.
59. The method of claim 48 wherein the solvent comprises an organic
solvent.
60. The method of claim 59 wherein the organic solvent is methanol,
ethanol, n-propanol, isopropanol, n-butanol, isobutanol,
sec-butanol, benzyl alcohol, glycerol, ethylene glycol, propylene
glycol, cresol, cyclohexanol, butyl Carbitol, Cellosolve, methyl
Cellosolve, ethyl lactate, acetone, methyl ethyl ketone, diethyl
ketone, methyl isobutyl ketone, cyclohexanone, acetophenone,
diethyl ether, isopropyl ether, furan, tetrahydrofuran, dioxane,
tetrahydropyran, methyl formate, ethyl formate, methyl acetate,
ethyl acetate, methyl propionate, ethyl propionate, methyl
butyrate, ethyl butyrate, propylene oxide, acetic acid, propionic
acid, butyrolactone, ethylene carbonate, propylene carbonate,
benzaldehyde, propyl amine, diethyl amine, ethanolamine, aniline,
pyridine, acetonitrile, dimethylformamide, propionitrile,
nitrobenzene, hexane, heptane, octane, nonane, decane, undecane,
dodecane, cyclohexane, benzene, toluene, xylene, mineral spirits,
kerosene, gasoline, carbon tetrachloride, chloroform, methylene
chloride, dichloroethane, trichloroethane, trichloroethylene,
chlorobenzene, Freon 113, Stoddard's solvent, carbon disulfide,
dimethyl sulfoxide, hexamethylphosphoric triamide, or combinations
thereof.
61. The method of claim 48 wherein the valence stabilizer is an
inorganic valence stabilizer or an organic valence stabilizer.
62. The method of claim 48 further comprising providing a
solubility control agent.
63. The method of claim 62 wherein the solubility control agent is
a cationic solubility control agent or an anionic solubility
control agent.
64. The method of claim 63 wherein the solubility control agent is
the cationic solubility control agent selected from H.sup.+;
Li.sup.+; Na.sup.+; K.sup.+; Rb.sup.+; Cs.sup.+; NH.sub.4.sup.+;
Mg.sup.+2; Ca.sup.+2; Sr.sup.+2; Be.sup.+2; Ba.sup.+2; Y.sup.+3;
La.sup.+3; Ce.sup.+3; Ce.sup.+4; Nd.sup.+3; Pr.sup.+3; Sc.sup.+3;
Sm.sup.+3; Eu.sup.+3; Eu.sup.+2; Gd.sup.+3; Tb.sup.+3; Dy.sup.+3;
Ho.sup.+3; Er.sup.+3; Tm.sup.+3; Yb.sup.+3; Lu.sup.+3; Ti.sup.+4;
Zr.sup.+4; Ti.sup.+3; Hf.sup.+4; Nb.sup.+5; Ta.sup.+5; Nb.sup.+4;
Ta.sup.+4; V.sup.+5; V.sup.+4; V.sup.+3; Mo.sup.+6; W.sup.+6;
Mo.sup.+5 W.sup.+5; Mo.sup.+4; W.sup.+4; Cr.sup.+3; Mn.sup.+2;
Mn.sup.+3; Mn.sup.+4; Fe.sup.+2; Fe.sup.+3; Co.sup.+2; Co.sup.+3;
Ni.sup.+2; Ni.sup.+3; Ni.sup.+4; Ru.sup.+2; Ru.sup.+3; R.sup.+4;
Rh.sup.'3; Ir.sup.+3; Rh.sup.+2; Ir.sup.+2; Pd.sup.+4; Pt.sup.+4;
Pd.sup.+2; Pt.sup.+2; Os.sup.+4; Cu.sup.+; Cu.sup.+2; Cu.sup.+3;
Ag.sup.+; Ag.sup.+2; Ag.sup.+3; Au.sup.+; Au.sup.+2; Au.sup.+3;
Zn.sup.+2; Cd.sup.+2; Hg.sup.+; Hg.sup.+2; Al.sup.+3; Ga.sup.+3;
Ga.sup.+; In.sup.+3; In.sup.+; Tl.sup.+3; Tl.sup.+; Ge.sup.+4;
Ge.sup.+2; Sn.sup.+4; Sn.sup.+2; Pb.sup.+4; Pb.sup.+2; Sb.sup.+3;
Sb.sup.+5; As.sup.+3; As.sup.+5; Bi.sup.+3; Bi.sup.+5; organic
compounds containing at least one N.sup.+ site; organic compounds
containing at least one phosphonium site; organic compounds
containing at least one arsonium site; organic compounds containing
at least one stibonium site; organic compounds containing at least
one oxonium site; organic compounds containing at least one
sulfonium site; organic compounds containing at least one
selenonium site; organic compounds containing at least one iodonium
site; quaternary ammonium compounds having a formula
NR.sub.4.sup.+, where R is an alkyl, aromatic, or acyclic organic
constituent; or combinations thereof.
65. The method of claim 64 wherein the cationic solubility control
agent is selected from H.sup.+; Li.sup.+; Na.sup.+; K.sup.+;
Rb.sup.+; Cs.sup.+; NH.sub.4.sup.+; Mg.sup.+2; Ca.sup.+2;
Sr.sup.+2; Y.sup.+3; La.sup.+3; Ce.sup.+3; Ce.sup.+4; Nd.sup.+3;
Pr.sup.+3; Sc.sup.+3; Sm.sup.+3; Eu.sup.+3; Eu.sup.+2; Gd.sup.+3;
Tb.sup.+3; Dy.sup.+3; Ho.sup.+3; Er.sup.+3; Tm.sup.+3; Yb.sup.+3;
Lu.sup.+3; Ti.sup.+4; Zr.sup.+4; Ti.sup.+3; Hf.sup.+4; Nb.sup.+5;
Ta.sup.+5; Nb.sup.+4; Ta.sup.+4; Mo.sup.+6; W.sup.+6; Mo.sup.+5;
W.sup.+5; Mo.sup.+4; W.sup.+4; Mn.sup.+2; Mn.sup.+3; Mn.sup.+4;
Fe.sup.+2; Fe.sup.+3; Co.sup.+2; Co.sup.+3; Ru.sup.+2; Ru.sup.+3;
Ru.sup.+4; Rh.sup.+3; Tl.sup.+3; Rh.sup.+2; Ir.sup.+2; Pd.sup.+4;
Pt.sup.+4; Pd.sup.+2; Pt.sup.+2; Cu.sup.+; Cu.sup.+2; Cu.sup.+3;
Ag.sup.+; Ag.sup.+2; Ag.sup.+3; Au.sup.+; Au.sup.+2; Au.sup.+3;
Zn.sup.+2; Al.sup.+3; Ga.sup.+3; Ga.sup.+; In.sup.+3; In.sup.+;
Ge.sup.+4; Ge.sup.+2; Sn.sup.+4; Sn.sup.+2; Sb.sup.+3; Sb.sup.+5;
Bi.sup.+3; Bi.sup.+5; organic compounds containing at least one
N.sup.+ site; organic compounds containing at least one phosphonium
site; organic compounds containing at least one stibonium site;
organic compounds containing at least one oxonium site; organic
compounds containing at least one sulfonium site; organic compounds
containing at least one iodonium site; quaternary ammonium
compounds having a formula NR.sup.4.sup.+, where R is an alkyl,
aromatic, or acyclic organic constituent; or combinations
thereof.
66. The method of claim 63 wherein the solubility control agent is
the anionic solubility control agent selected from fluorotitanates,
chlorotitanates, fluorozirconates, chlorozirconates,
fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates,
molybdates, tungstates, permanganates, fluoromanganates,
chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates,
chlorocobaltates, fluorozincates, chlorozincates, borates,
fluoroborates, fluoroaluminates, chloroaluminates, carbonates,
silicates, fluorosilicates, fluorostannates, nitrates, nitrites,
azides, cyanamides, phosphates, phosphites, phosphonates,
phosphinites, thiophosphates, thiophosphites, thiophosphonates,
thiophosphinites, fluorophosphates, fluoroantimonates,
chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates,
dithionites, dithionates, fluorosulfates, tellurates, fluorides,
chlorides, chlorates, perchlorates, bromides, bromates, iodides,
iodates, periodates, heteropolyanions, ferricyanides,
ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates,
cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates,
cyanatomanganates, thiocyanates, thiocyanatoferrates,
thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates,
cyanamides, cyanamidoferrates, cyanamidocobaltates,
cyanamidocuprates, cyanamidomanganates, nitritoferrates,
nitritocobaltates, azides, (thio)carboxylates,
di(thio)carboxylates, tri(thio)carboxylates,
tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates,
tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates,
di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides,
di(thio)phosphonamides, tri(thio)phosphonamides,
amino(thio)phosphonates, diamino(thio)phosphonates,
triamino(thio)phosphonates, imino(thio)phosphonates,
diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates,
tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides,
tri(thio)sulfonamides, amino(thio)sulfonates,
diamino(thio)sulfonates, triamino(thio)sulfonates,
imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates,
di(thio)borates, (thio)boronates, organic silicates, stibonates,
cyanides, cyanochromates, cyanonickelates, cyanatochromates,
cyanatonickelates, thiocyanatochromates, thiocyanatonickelates,
cyanamidochromates, cyanamidonickelates, nitritonickelates,
arsonates, diarsonates, triarsonates, organic selenates,
diselenates, triselenates, arsenates, arsenites, fluoroarsenates,
chloroarsenates, selenates, selenites, fluorothallates,
chlorothallates, iodomercury anions, chloromercurates,
bromomercurates, osmates, fluoronickelates, chromates, Reinecke's
salt, vanadates, or combinations thereof.
67. The method of claim 66 wherein the anionic solubility control
agent is selected from fluorotitanates, chlorotitanates,
fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates,
fluorotantalates, chlorotantalates, molybdates, tungstates,
permanganates, fluoromanganates, chloromanganates, fluoroferrates,
chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates,
chlorozincates, borates, fluoroborates, fluoroaluminates,
chloroaluminates, carbonates, silicates, fluorosilicates,
fluorostannates, nitrates, nitrites, azides, cyanamides,
phosphates, phosphites, phosphonates, phosphinites, thiophosphates,
thiophosphites, thiophosphonates, thiophosphinites,
fluorophosphates, fluoroantimonates, chloroantimonates, sulfates,
sulfites, sulfonates, thiosulfates, dithionites, dithionates,
fluorosulfates, tellurates, fluorides, chlorides, chlorates,
perchlorates, bromides, bromates, iodides, iodates, periodates,
heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates,
cyanocuprates, cyanomanganates, cyanates, cyanatoferrates,
cyanatocobaltates, cyanatocuprates, cyanatomanganates,
thiocyanates, thiocyanatoferrates, thiocyanatocobaltates,
thiocyanatocuprates, thiocyanatomanganates, cyanamides,
cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates,
cyanamidomanganates, nitritoferrates, nitritocobaltates, azides,
(thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates,
tetra(thio)carboxylates, (thio)phenolates, di (thio)phenolates,
tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates,
di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides,
di(thio)phosphonami des, tri(thio)phosphonamides,
amino(thio)phosphonates, diamino(thio)phosphonat- es,
triamino(thio)phosphonates, imino(thio)phosphonates,
diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates,
tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides,
tri(thio)sulfonamides, amino(thio)sulfonates,
diamino(thio)sulfonates, triamino(thio)sulfonates,
imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates,
di(thio)borates, (thio)boronates, organic silicates, stibonates, or
combinations thereof.
68. The method of claim 48 wherein the valence stabilizer is
provided by adding it to the manganese solution.
69. The method of claim 48 wherein the valence stabilizer is
provided as a separate solution.
70. The method of claim 62 wherein the solubility control agent is
provided by adding the solubility control agent to the manganese
solution.
71. The method of claim 62 whereby the solubility control agent is
provided by adding the solubility control agent to a separate
solution containing the valence stabilizer.
72. The method of claim 62 wherein the solubility control agent is
provided as a separate solution.
73. The method of claim 48 further comprising heating the manganese
solution.
74. The method of claim 48 further comprising cooling the manganese
solution.
75. The method of claim 48 further comprising adjusting the pH of
the manganese solution using a compound selected from acids or
bases.
76. The method of claim 48 further comprising adsorbing or mixing
the manganese/valence stabilizer complex onto, into, or with an
inert medium selected from oxides, hydroxides, phosphates, borates,
silicates, carbonates, aluminates, titanates, molybdates,
tungstates, oxalates, polymers, or combinations thereof.
77. A method of making a corrosion-inhibiting pigment comprising:
providing a manganese source; providing a valence stabilizer; and
heating the manganese source and the valence stabilizer in an
oxidizing environment to form a pigment containing trivalent or
tetravalent manganese.
78. The method of claim 77 wherein the manganese source is selected
from divalent manganese sources, trivalent manganese sources,
tetravalent manganese sources, heptavalent manganese sources, or
combinations thereof.
79. The method of claim 77 wherein the manganese source is selected
from manganese oxide, manganese dioxide, manganomanganic oxide,
manganese sesquioxide, manganese hydroxide, manganese carbonate,
manganese silicate, manganese borate, manganese sulfide, manganese
phosphate, lithiated manganese spinel, manganese oxalate, manganese
nitrate, manganese sulfate, manganese perchlorate, manganese
chloride, manganese fluoride, manganese bromide, manganese iodide,
manganese bromate, manganese chlorate, manganese fluosilicate,
manganese fluotitanate, manganese fluozirconate, manganese
fluoborate, manganese fluoaluminate, manganese formate, manganese
acetate, manganese propionate, manganese butyrate, manganese
valerate, manganese benzoate, manganese glycolate, manganese
lactate, manganese tartronate, manganese malate, manganese
tartrate, manganese citrate, manganese benzenesulfonate, manganese
thiocyanate, manganese acetylacetonate, potassium penmanganate,
sodium permanganate, lithium permanganate, ammonium penmanganate,
magnesium permanganate, calcium permanganate, strontium
permanganate, barium permanganate, zinc permanganate, ferric
permanganate, nickel permanganate, copper penmanganate, cobalt
penmanganate, cerium penmanganate, lanthanum permanganate, yttrium
penmanganate, aluminum permanganate, or combinations thereof.
80. The method of claim 77 wherein the manganese source is a
precipitate or a mineral.
81. The method of claim 80 wherein the manganese mineral is
selected from manganosite, pyrochroite, rhodochrosite, rhodonite,
tephroite, manganhumite, manganjustite, alabandite, hauerite,
reddingite, hureaulite, pyrolusite, hausmannite, manganite,
ramsdellite, bixbyite, groutite, feitknechite, akhtenskite,
buserite, nsutite, hetaerolite, marokite, hydrohetaerolite,
braunite, psilomelane, romanechite, cryptomelane, manjiroite,
lithiophorite, chalcophanite, hollandite, neltnerite, woodruffite,
birnesite, asbolane, todorokite, vernadite, or combinations
thereof.
82. The method of claim 77 wherein the valence stabilizer is
oxygen.
83. The method of claim 77 wherein the oxidizing environment is
selected from oxygen, air, ozone, nitrogen oxides, sulfur oxides,
chlorine, fluorine, or combinations thereof.
84. The method of claim 83 wherein the oxidizing environment is
selected from oxygen, air, or combinations thereof.
85. The method of claim 77 wherein the manganese-containing mixture
is heated to between about 200.degree. C. and about 1200.degree.
C.
86. The method of claim 77 further comprising providing a
solubility control agent.
87. The method of claim 86 wherein the solubility control agent is
a cationic solubility control agent selected from Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, Be.sup.+2, Mg.sup.+2,
Ca.sup.+2, Sr.sup.'2, Ba.sup.+2, Y.sup.+3, La.sup.+3, Ce.sup.+3,
Ce.sup.+4, Ti.sup.+4, Zr.sup.+4, V.sup.+5, Nb.sup.+5, Ta.sup.+5,
Mo.sup.+6, W.sup.+6, Cr.sup.+3, Mn.sup.+2, Fe.sup.+3, Fe.sup.+2,
Co.sup.+2, Co.sup.+3, Ni.sup.+2, Cu.sup.+2, Ag.sup.+, Ag.sup.+2,
Zn.sup.+2, Al.sup.+3, In.sup.+3, Sn.sup.+4, Sb.sup.+3, Sb.sup.+5,
Bi.sup.+3, Bi.sup.+5, or combinations thereof.
88. The method of claim 87 wherein the cationic solubility control
agent is selected from Ba.sup.+2, Bi.sup.+3, Bi.sup.+5, or
combinations thereof.
89. The method of claim 86 wherein the solubility control agent is
provided by adding the solubility control agent to the
manganese-containing mixture.
90. The method of claim 77 further comprising mixing the
manganese/valence stabilizer complex onto, into, or with an inert
medium selected from oxides, hydroxides, phosphates, borates,
silicates, carbonates, aluminates, titanates, molybdates,
tungstates, oxalates, or combinations thereof.
91. A method for treating a surface for corrosion resistance,
comprising: providing a substrate to be coated; and applying a
corrosion-inhibiting pigment comprising manganese, where the
manganese is trivalent manganese, tetravalent manganese, or
combinations thereof, and a valence stabilizer combined to form a
manganese/valence stabilizer complex.
92. The method of claim 91 wherein the substrate is subject to
water-based electrochemical corrosion.
93. The method of claim 91 wherein the manganese/valence stabilizer
complex has a solubility in water of between about 1.times.10.sup.0
and about 1.times.10.sup.-17 moles per liter of manganese at about
25.degree. C. and about 760 Torr.
94. The method of claim 93 wherein the solubility of the
manganese/valence stabilizer complex in water is between about
1.times.10.sup.-1 and about 1.times.10.sup.4 moles per liter of
manganese at about 25.degree. C. and about 760 Torr.
95. The method of claim 93 wherein the solubility of the
manganese/valence stabilizer complex in water is between about
1.times.10.sup.-6 and about 1.times.10.sup.-8 moles per liter of
manganese at about 25.degree. C. and about 760 Torr.
96. The method of claim 93 wherein the solubility of the
manganese/valence stabilizer complex in water is between about
1.times.10.sup.-9 and about 1.times.10.sup.17 moles per liter of
manganese at about 25.degree. C. and about 760 Torr.
97. The method of claim 91 wherein there is an electrostatic
barrier layer around the manganese/valence stabilizer complex in
aqueous solution.
98. The method of claim 91 wherein the manganese/valence stabilizer
complex acts as an ion exchange agent towards corrosive ions.
99. The method of claim 91 wherein the manganese/valence stabilizer
complex decomposes at a temperature above about 100.degree. C.
100. The method of claim 91 wherein the manganese/valence
stabilizer complex melts at a temperature above about 50.degree.
C.
101. The method of claim 91 wherein the valence stabilizer is an
inorganic valence stabilizer or an organic valence stabilizer.
102. The method of claim 93 wherein the manganese/valence
stabilizer complex further comprises a solubility control
agent.
103. The method of claim 102 wherein the solubility control agent
is a cationic solubility control agent or an anionic solubility
control agent.
104. The method of claim 103 wherein the solubility control agent
is the cationic solubility control agent selected from H.sup.+;
Li.sup.+; Na.sup.+; K.sup.+; Rb.sup.+; Cs.sup.+; NH.sub.4.sup.+;
Mg.sup.+2; Ca.sup.+2; Sr.sup.+2; Be.sup.+2; Ba.sup.+2; Y.sup.+3;
La.sup.+3; Ce.sup.+3; Ce.sup.+4; Nd.sup.+3; Pr.sup.+3; Sc.sup.+3;
Sm.sup.+3; Eu.sup.+3; Eu.sup.+2; Gd.sup.+3; Tb.sup.+3; Dy.sup.+3;
Ho.sup.+3; Er.sup.+3; Tm.sup.+3; Yb.sup.+3; Lu.sup.+3; Ti.sup.+4;
Zr.sup.+4; Ti.sup.+3; Hf.sup.+4; Nb.sup.+5; Ta.sup.+5; Nb.sup.+4;
Ta.sup.+4; V.sup.+5; V.sup.+4; V.sup.+3; Mo.sup.+6; W.sup.+6;
Mo.sup.+5; W.sup.+5; Mo.sup.+4; W.sup.+4; Cr.sup.+3; Mn.sup.+2;
Mn.sup.+3; Mn.sup.+4; Fe.sup.+2; Fe.sup.+3; Co.sup.+2; Co.sup.+3;
Ni.sup.+2; Ni.sup.+3; Ni.sup.+4; Ru.sup.+2; Ru.sup.+3; Ru.sup.+4;
Rh.sup.+3; Ir.sup.+3; Rh.sup.+2; Ir.sup.+2; Pd.sup.+4; Pt.sup.+4;
Pd.sup.+2; Pt.sup.+2; Os.sup.+4; Cu.sup.+; Cu.sup.+2; Cu.sup.+3;
Ag.sup.+; Ag.sup.+2; Ag.sup.3; Au.sup.+; Au.sup.+2; Au.sup.+3;
Zn.sup.+2; Cd.sup.+2; Hg.sup.+; Hg.sup.+2; Al.sup.+3; Ga.sup.+3;
Ga.sup.+; In.sup.+3; In.sup.+; Tl.sup.+3; Tl.sup.+; Ge.sup.+4;
Ge.sup.+2; Sn.sup.+4; Sn.sup.+2; Pb.sup.+4; Pb.sup.+2; Sb.sup.+3;
Sb.sup.+5; As.sup.+3; As.sup.+5; Bi.sup.+3; Bi.sup.+5; organic
compounds containing at least one N.sup.+ site; organic compounds
containing at least one phosphonium site; organic compounds
containing at least one arsonium site; organic compounds containing
at least one stibonium site; organic compounds containing at least
one oxonium site; organic compounds containing at least one
sulfonium site; organic compounds containing at least one
selenonium site; organic compounds containing at least one iodonium
site; quaternary ammonium compounds having a formula
NR.sup.4.sup.+, where R is an alkyl, aromatic, or acyclic organic
constituent; or combinations thereof.
105. The method of claim 104 wherein the cationic solubility
control agent is selected from H.sup.+; Li.sup.+; Na.sup.+;
K.sup.+; Rb.sup.+; Cs.sup.+; NH.sub.4.sup.+; Mg.sup.2; Ca.sup.+2;
Sr.sup.+2; Y.sup.+3; La.sup.+3; Ce.sup.+3 Ce.sup.+4; Nd.sup.+3;
Pr.sup.+3; Sc.sup.+3; Sm.sup.+3; Eu.sup.+3; Eu.sup.+2; Gd.sup.+3;
Tb.sup.+3; Dy.sup.+3; Ho.sup.+3; Er.sup.+3; Tm.sup.+3; Yb.sup.+3;
Lu.sup.+3; Ti.sup.+4; Zr.sup.+4; Ti.sup.+3; Hf.sup.+4; Nb.sup.+5;
Ta.sup.+5; Nb.sup.+4; Ta.sup.+4; Mo.sup.+6; W.sup.+6; Mo.sup.+5;
W.sup.+5; Mo.sup.+4; W.sup.+4; Mn.sup.+2; Mn.sup.+3; Mn.sup.+4;
Fe.sup.+2; Fe.sup.+3; Co.sup.+2; Co.sup.+3; Ru.sup.+2; Ru.sup.+3;
Ru.sup.+4; Rh.sup.+3; Ir.sup.+3; Rh.sup.+2; Ir.sup.+2; Pd.sup.+4;
Pt.sup.+4; Pd.sup.+2; Pt.sup.+2; Cu.sup.+; Cu.sup.+2; Cu.sup.+3;
Ag.sup.+; Ag.sup.+2; Ag.sup.+3; Au.sup.+; Au.sup.+2; Au.sup.+3;
Zn.sup.+2; Al.sup.+3; Ga.sup.+3; Ga.sup.+; In.sup.+3; In.sup.+;
Ge.sup.+4; Ge.sup.+2; Sn.sup.+4; Sn.sup.+2; Sb.sup.+3; Sb.sup.+5;
Bi.sup.+3; Bi.sup.+5; organic compounds containing at least one
N.sup.+ site; organic compounds containing at least one phosphonium
site; organic compounds containing at least one stibonium site;
organic compounds containing at least one oxonium site; organic
compounds containing at least one sulfonium site; organic compounds
containing at least one iodonium site; quaternary ammonium
compounds having a formula NR.sup.4.sup.+, where R is an alkyl,
aromatic, or acyclic organic constituent; or combinations
thereof.
106. The method of claim 103 wherein the solubility control agent
is the anionic solubility control agent is selected from
fluorotitanates, chlorotitanates, fluorozirconates,
chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates,
chlorotantalates, molybdates, tungstates, permanganates,
fluoromanganates, chloromanganates, fluoroferrates, chloroferrates,
fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates,
borates, fluoroborates, fluoroaluminates, chloroaluminates,
carbonates, silicates, fluorosilicates, fluorostannates, nitrates,
nitrites, azides, cyanamides, phosphates, phosphites, phosphonates,
phosphinites, thiophosphates, thiophosphites, thiophosphonates,
thiophosphinites, fluorophosphates, fluoroantimonates,
chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates,
dithionites, dithionates, fluorosulfates, tellurates, fluorides,
chlorides, chlorates, perchlorates, bromides, bromates, iodides,
iodates, periodates, heteropolyanions, ferricyanides,
ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates,
cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates,
cyanatomanganates, thiocyanates, thiocyanatoferrates,
thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates,
cyanamides, cyanamidoferrates, cyanamidocobaltates,
cyanamidocuprates, cyanamidomanganates, nitritoferrates,
nitritocobaltates, azides, (thio)carboxylates,
di(thio)carboxylates, tri(thio)carboxylates,
tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates,
tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates,
di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides,
di(thio)phosphonamides, tri(thio)phosphonamides,
amino(thio)phosphonates, diamino(thio)phosphonates,
triamino(thio)phosphonates, imino(thio)phosphonates,
diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates,
tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides,
tri(thio)sulfonamides, amino(thio)sulfonates,
diamino(thio)sulfonates, triamino(thio)sulfonates,
imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates,
di(thio)borates, (thio)boronates, organic silicates, stibonates,
cyanides, cyanochromates, cyanonickelates, cyanatochromates,
cyanatonickelates, thiocyanatochromates, thiocyanatonickelates,
cyanamidochromates, cyanamidonickelates, nitritonickelates,
arsonates, diarsonates, triarsonates, organic selenates,
diselenates, triselenates, arsenates, arsenites, fluoroarsenates,
chloroarsenates, selenates, selenites, fluorothallates,
chlorothallates, iodomercury anions, chloromercurates,
bromomercurates, osmates, fluoronickelates, chromates, Reinecke's
salt, vanadates, or combinations thereof.
107. The method of claim 103 wherein the anionic solubility control
agent is selected from fluorotitanates, chlorotitanates,
fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates,
fluorotantalates, chlorotantalates, molybdates, tungstates,
permanganates, fluoromanganates, chloromanganates, fluoroferrates,
chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates,
chlorozincates, borates, fluoroborates, fluoroaluminates,
chloroaluminates, carbonates, silicates, fluorosilicates,
fluorostannates, nitrates, nitrites, azides, cyanamides,
phosphates, phosphites, phosphonates, phosphinites, thiophosphates,
thiophosphites, thiophosphonates, thiophosphinites,
fluorophosphates, fluoroantimonates, chloroantimonates, sulfates,
sulfites, sulfonates, thiosulfates, dithionites, dithionates,
fluorosulfates, tellurates, fluorides, chlorides, chlorates,
perchlorates, bromides, bromates, iodides, iodates, periodates,
heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates,
cyanocuprates, cyanomanganates, cyanates, cyanatoferrates,
cyanatocobaltates, cyanatocuprates, cyanatomanganates,
thiocyanates, thiocyanatoferrates, thiocyanatocobaltates,
thiocyanatocuprates, thiocyanatomanganates, cyanamides,
cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates,
cyanamidomanganates, nitritoferrates, nitritocobaltates, azides,
(thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates,
tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates,
tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates,
di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides,
di(thio)phosphonamides, tri(thio)phosphonamides,
amino(thio)phosphonates, diamino(thio)phosphonat- es,
triamino(thio)phosphonates, imino(thio)phosphonates,
diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates,
tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides,
tri(thio)sulfonamides, amino(thio)sulfonates,
diamino(thio)sulfonates, triamino(thio)sulfonates,
imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates,
di(thio)borates, (thio)boronates, organic silicates, stibonates, or
combinations thereof.
108. The method of claim 100 wherein the manganese/valence
stabilizer complex is adsorbed onto, into, or mixed with an inert
medium selected from oxides, hydroxides, phosphates, borates,
silicates, carbonates, aluminates, titanates, molybdates,
tungstates, oxalates, polymers, or combinations thereof.
109. The method of claim 91 wherein the pigment is colored.
110. The method of claim 91 wherein the pigment exhibits a color
change between manganese oxidation states.
111. The method of claim 91 wherein the pigment is light-fast.
112. The method of claim 91 wherein the substrate is selected from
metals, semimetals, semiconductors, composite materials with
anisotropic electrical conductivity, or materials in a conductive
or dielectric medium.
113. The method of claim 91 further comprising surface treating the
substrate before applying the pigment.
114. The method of claim 91 further comprising applying a coating
to the substrate before applying the pigment.
115. The method of claim 91 further comprising applying a coating
concurrently with applying the pigment.
116. The method of claim 91 further comprising applying a coating
to the substrate, the coating selected from organic coatings,
inorganic coatings, or combinations thereof.
117. The method of claim 116 wherein the coating is the organic
coating selected from alkyd-type primers, acrylic primers,
oil-based primers, polyester primers, epoxy primers, conductive
primers, organic sol-gels, ketimine coatings, polyvinyl coatings,
acrylic thermoplastics, asphaltic and coal tar thermoplastics,
polyamide thermoplastics, polyethylene dispersion thermoplastics,
fluorocarbon thermoplastics, chlorocarbon thermoplastics, silicone
thermosets, polyurethane thermosets, polyester thermosets,
epoxy-amine thermosets, epoxy-amide thermosets, epoxy-ester
thermosets, epoxy-coal tar thermosets, furane thermosets, phenolic
thermosets, butadiene styrene elastomers, chlorinated rubber
elastomers, polysulfonated elastomers, neoprene elastomers, or
combinations thereof.
118. The method of claim 116 wherein the coating is the inorganic
coating selected from low temperature enamels, low temperature
glass frits, carbonaceous coatings, zeolites, inorganic sol-gels,
or combinations thereof.
119. A corrosion-inhibiting pigment comprising manganese, wherein
the manganese is trivalent manganese, tetravalent manganese, or
combinations thereof, and a valence stabilizer combined to form a
manganese/valence stabilizer complex, wherein the manganese/valence
stabilizer complex is sparingly soluble, exhibits low solubility,
or is insoluble in water at about 25.degree. C. and about 760
Torr.
120. A method of making a corrosion-inhibiting pigment comprising:
providing a solvent; providing a manganese source in the solvent
forming a manganese solution; providing a valence stabilizer; and
combining the manganese source and the valence stabilizer to form a
manganese/valence stabilizer complex, wherein the manganese/valence
stabilizer complex is sparingly soluble in water at about
25.degree. C. and about 760 Torr.
121. A method of making a corrosion-inhibiting pigment comprising:
providing a manganese source; providing a valence stabilizer; and
heating the manganese source and the valence stabilizer in an
oxidizing environment to form a pigment containing trivalent or
tetravalent manganese, wherein the trivalent manganese or
tetravalent manganese compound exhibits low solubility or
insolubility in water at about 25.degree. C. and about 760
Torr.
122. A method for treating a surface for corrosion resistance,
comprising: providing a substrate to be coated; and applying a
manganese-inhibiting pigment comprising manganese, wherein the
manganese is trivalent manganese, tetravalent manganese, or
combinations thereof, and a valence stabilizer combined to form a
manganese/valence stabilizer complex, wherein the manganese/valence
stabilizer complex is sparingly soluble in water at about
25.degree. C. and about 760 Torr.
123. A method for treating a surface for corrosion resistance,
comprising: providing a substrate to be coated; and applying a
manganese-inhibiting pigment comprising manganese, wherein the
manganese is trivalent manganese, tetravalent manganese, or
combinations thereof, and oxygen combined to form a manganese
compound wherein the manganese/valence stabilizer complex exhibits
low solubility or insolubility in water at about 25.degree. C. and
about 760 Torr.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to commonly assigned U.S. patent
application Ser. No. ______, (Attorney Docket No. UVD 0318 PA)
NON-TOXIC CORROSION--PROTECTION PIGMENTS BASED ON PERMANGANATE AND
MANGANATE, filed Jan. 13, 2003 by Sturgill et al., the disclosure
of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates generally to compositions and methods
for the formation of protective, corrosion-inhibiting pigments
without the use of chromium in the hexavalent oxidation state or
lead in the tetravalent oxidation state. More particularly, this
invention relates to non-toxic, corrosion-inhibiting pigments based
on trivalent and tetravalent manganese and methods of making and
using the same.
[0003] Inhibiting the initiation, growth, and extent of corrosion
is a significant part of component and systems design for the
successful long-term use of metal objects. Uniform physical
performance and safety margins of a part, a component, or an entire
system can be compromised by corrosion. Aluminum, zinc, iron,
magnesium, titanium and their alloys tend to corrode rapidly in the
presence of water due to their low oxidation-reduction (redox)
potentials. The high strength 2000 and 7000 series of aluminum
alloys are used extensively in aircraft and are very sensitive to
corrosive attack. Materials such as steels and carbon fibers with
higher redox potentials will form a galvanic couple in water and
promote corrosive attack when located near light metal alloys such
as aluminum.
[0004] A bare metal surface or one that has been conversion coated,
phosphated, sealed, rinsed, or otherwise treated will be protected
by the application of a primer paint with a corrosion inhibiting
pigment. As used herein, the term "pigment" means chemically active
compounds with the ability to inhibit corrosion at a distance,
rather than simple colorants or opacifiers. Oxidative compounds
that are effective as corrosion inhibitors tend to be highly
colored and/or opaque. An effective corrosion inhibiting pigment
has throwing power and can protect exposed base metal in a scratch
or flaw by oxidizing and passivating it at a distance during
aqueous corrosion when dispersed in a suitable carrier phase. These
compounds are usually solids or liquids that are typically
dispersed in a liquid carrier or binder system such as a paint or
wash. These compounds may also be used to help inhibit corrosion
without a significant liquid carrier using an integral binder
and/or a low-volatile application method. Barrier layer formers
such as sol-gel coatings or polymeric films are also used, but they
tend to have no inherent oxidizing character and no appreciable
throwing power and fail to protect the metal surface when the film
is breached.
[0005] Pigments that contain hexavalent chromium (CrVI) compounds
are the de facto standard for high-performance corrosion inhibiting
paints and coatings for metal protection and are a typical
corrosion inhibitor used to protect aluminum, zinc, magnesium,
iron, titanium, copper and their alloys. Zinc (C.I. Pigment Yellow
36) and strontium (C.I. Pigment Yellow 32) chromate pigments are
typically used, although higher-solubility calcium and magnesium
chromates have also seen some limited use as pigments. The coating
vehicles of these pigments include alkyd-type primers, acrylic
primers, and elastomeric sealants, among others. Some transition
metal chromate pigments (e.g., complexed with copper, iron,
manganese, or cobalt) and organic chromate pigments (e.g., bound
with nitrogenous compounds such as guanidinium) have been used in
protective coating systems. Barium or lead chromates have also been
used as corrosion inhibitors, as well as colorants. Variations in
chromate speciation (i.e., what the chromate ions are bound to)
will result in significant differences in protection when used as
corrosion-inhibiting pigments, due to differences in chromate
solubility.
[0006] A clear correlation between performance and solubility of
chromate pigments has been shown. However, oxidizing chromates can
be dangerous to use as corrosion inhibitors if they are not
delivered in sufficient quantity in a timely manner to the location
of a coating breach. The chromate composition was far more
important to the corrosion inhibiting performance of the primer
film than the organic coating composition.
[0007] A principle use of zinc and strontium chromate pigments is
in wash- or etch-primer formulations for aluminum protection. Wash-
or etch-primers, which have been used since the 1940s, represent
one of the harshest application conditions for chromate pigments.
Wash-primers are applied to metal surfaces under acidic conditions
where the primer is cured as a corrosion inhibiting film. Chromate
pigment powders dispersed in an alcohol/resin base mixture are
combined with an aqueous phosphoric acid diluent solution. The acid
roughens the metal surface and initiates cross-linking of the resin
to form a pigment-filled polymeric film. The chromate pigment may
also be dispersed in other carriers that are not as harsh as the
wash primer. However, if a corrosion-inhibiting pigment can survive
the harsh conditions of acid diluent, then it can usually be
successfully incorporated within other paint, polymeric, or barrier
film systems for corrosion inhibition.
[0008] An important use of chromate pigments is in coil coating
formulations for steel, zinc-coated steel, or aluminum sheet stock.
Coil coatings can represent a challenging application environment
for pigments in that cure temperatures for these paints can exceed
100 C. Corrosion-inhibiting pigments for these applications must
exhibit both throwing power to inhibit corrosion and be thermally
stable at elevated temperatures when incorporated into the
paint.
[0009] Lead chromate pigments of various compositions are mostly
used as colorants, although they are also used for corrosion
protection, albeit often for different applications than zinc or
strontium chromates. This is necessitated by the much lower
solubility of lead chromate in comparison to these other chromates.
The dark yellow lead chromate (PbCrO.sub.4, C.I. Pigment Yellow 34)
exhibits a solubility of approximately 10.sup.-7 moles/liter
Cr.sup.+6, whereas the darker basic lead chromate (PbCrO.sub.4.PbO,
C.I. Pigment Orange 21) exhibits slightly lower solubility in
water. In addition, lead chromate can be combined with other lead
compounds to alter the spectral or solubility characteristics. For
example, the lemon yellow lead silicochromate
(PbCrO.sub.4.PbSiO.sub.3) and reddish lead molybdate-chromate
(PbCrO.sub.4.PbMoO.sub.4, C.I. Pigment Red 104) are representative
examples. [Note: This same situation exists for zinc chromate
pigments such as ZnCrO.sub.4, ZnCrO.sub.4.Zn(OH).sub.2, and
ZnCrO.sub.4(OH).Zn(OH).sub.2, wherein increased basicity leads to
lowering of the solubility.]
[0010] While lead chromate can be used in some of the same coating
vehicles as zinc or strontium chromate (i.e., alkyd-type primers),
the much lower solubility of lead chromate permits its use in
binder systems for which zinc or strontium chromate would be
unsuitable. For example, lead chromate is often used in oil-based
paints (i.e., linseed oil) wherein greater than 75% by weight of
the paint system is pigment. The mechanistic action of the divalent
lead ion present in the lead chromate pigments is discussed
below.
[0011] Pigments that contain tetravalent lead (PbIV) are also used
extensively in coatings for metal protection, especially for steels
and cast irons. The most notable PbIV pigment is red lead
(Pb.sub.3O.sub.4, C.I. Pigment Red 105). Red lead is
compositionally equivalent to lead plumbate
[(Pb.sup.2+).sub.2(PbO.sub.44.sup.4-)], wherein only one of the
constituent lead atoms is in the tetravalent oxidation state, while
the other two are present as the more common divalent species. The
PbVI solubility for this compound is a remarkably low 10.sup.-17
moles/liter Pb.sup.+4 (Glasstone, J. Chem. Soc. 121: 1456-69,
1922), implying an extremely low release rate of PbIV. Red lead is
used primarily in alkyd-type primers as well as oil-based paints
such as those containing linseed oil.
[0012] Calcium plumbate (Ca.sub.2PbO.sub.4, Caldiox.TM.) is another
representative example of a corrosion-inhibiting pigment containing
PbIV. Due to its higher solubility in comparison to red lead,
calcium plumbate is most frequently used for applications where a
quicker release of oxidizing ions is necessary for protection, such
as on galvanized steel. Calcium plumbate is most frequently used in
alkyd-type or acrylic primers.
[0013] The use of hexavalent chromium or tetravalent lead pigments
allows a broad range of service conditions to be addressed by
tailoring the solubility of the pigment to the application needs.
Very low solubility pigments, such as red lead, employ other
corrosion-inhibiting mechanisms in addition to oxidative
passivation. The divalent lead ions present in red lead (and even
lead chromate) have been observed to form "lead soaps" after long
storage when the pigment is used in conjunction with oil paints,
especially those comprised of linseed oil. "Lead soaps" are
reaction products between the alkaline divalent lead ions and the
long-chain carboxylic acids present (i.e., oleates, linoleates,
linolenates, palmitates, and stearates). This indicates that even
though these pigments exhibit low solubility in water, the
constituent ions are still chemically active, but less than their
more soluble cousins. The divalent lead ions form insoluble
compounds with corrosive anions such as sulfate, and low-solubility
compounds with other corrosive ions such as chloride, thereby
effectively removing them from the corroding system. For the
heavier, more insoluble lead pigments such as red lead and basic
lead chromate, the inhibiting action is due to both the oxidative
tetravalent lead or hexavalent chromium ions, and the ability of
the divalent lead ions to `capture` (insolubilize) corrosive anions
such as sulfate.
[0014] Significant efforts have been made in government and
industry to replace CrVI and PbIV with other metals for
corrosion-inhibiting applications due to toxicity, environmental,
and regulatory considerations. An effective replacement for
hexavalent chromate or tetravalent lead pigment needs to have
throwing power for self-healing coating breeches. Throwing power is
the ability of a highly oxidized ion, such as hexavalent chromium
or tetravalent lead, to oxidize and passivate the exposed bare
metal in a small scratch or flaw.
[0015] A number of materials have been introduced as
corrosion-inhibiting replacement pigments for tetravalent lead- or
hexavalent chromium-based compounds. Commercially available
corrosion inhibiting pigments including compounds such as
molybdates, phosphates, silicates, cyanamides, and borates that
have no inherent oxidizing character have been used as alternatives
to chromate pigments. Coatings that contain these materials can
effectively inhibit corrosion as barrier films until the coating is
breached, as by a scratch or other flaw. Films or coatings that do
not contain oxidizing species can actually enhance corrosion on a
surface after failure due to the effects of crevice corrosion.
[0016] Manganese is one non-toxic, non-regulated metal which has
been considered as a chromium or lead replacement. Manganese (like
chromium or lead) exhibits more than one oxidation state
(Mn.sup.+2, Mn.sup.+3, and Mn.sup.+4). In addition, the
oxidation-reduction potential is comparable to that of CrVI or PbIV
in acidic solutions. For example, in acid solution:
Mn.sup.+3+e.sup.-Mn.sup.+2+1.49 V
Mn.sup.+4+e.sup.-Mn.sup.+3+1.65V
Cr.sup.+6+3e.sup.-Cr.sup.+3+1.36 V
Pb.sup.+4+2e.sup.-Pb.sup.+2+1.70 V
[0017] The MnIV and MnIII ions are very good oxidizing species with
oxidation-reduction potentials of +1.65 V and +1.49 V (at pH 0),
respectively. The hydroxyl and oxygen liberated from water when
MnIV or MnIII is reduced will oxidize nearby bare metal. This
results in a passivated metal surface if sufficient oxygen is
released. The potential required to reduce tetravalent or trivalent
manganese to divalent manganese is only 0.29 or 0.13 volts greater
than that needed to add three electrons to reduce CrVI to trivalent
chromium (CrIII). Although neither MnIV or MnIII match PbIV in
terms of redox potential, neither is significantly lower and so
comparable passivation of metal is achieved. MnII is formed during
corrosion inhibition by the oxidation of base metal in the presence
of MnIV or MnIII and water. MnII is similar to CrIII in that
neither is particularly effective as redox-based corrosion
inhibitors.
[0018] A number of pigments using manganese have been reported in
the literature over the years, but none approach the general
performance or utility of PbIV- or CrVI-based pigments. For
example, Manganese Violet is a colorant composed of MnII
pyrophosphate with no oxidizing characteristics.
[0019] A number of compounds have been described as
corrosion-inhibiting agents, including organic mercapto and thio
compounds, cyclic tetraaza compounds, aminophosphonic acid, and
triazinedithiols and triazinetrithiols. Other compounds have been
described as corrosion inhibiting when complexed with manganese,
typically in the divalent charge state. Among these compounds are
porphyrin derivatives, tetraaza organic compounds, phosphoric and
phosphonic acids, naphthenates, amidosulfonic acids, and amino
acids. However, the pigments formed from these compounds provide
only limited corrosion protection and do not approach the benefit
derived from the use of hexavalent chromium.
[0020] In addition, the formation of manganese-containing pigments
in which the manganese is complexed with ligands such as
hydrazones, O bidentates, azomethines, phthalocyanines, azo and
disazo complexes, N--S bidentates, oximes, tetraaza complexes,
porphyrins, 1,2-dithiolates, and semicarbazones, has also been
described. However, these compounds do not use tetravalent or
trivalent manganese and are not used for anticorrosive
applications.
[0021] U.S. Pat. No. 6,416,868 to Sullivan, et al. describes the
use of alkaline earth-manganese oxides as pigments, wherein the
alkaline earth is selected from Mg, Ca, Sr, and Ba. The pigments
are described as being colorants and as resisting heat build-up due
to infrared reflectance. Corrosion inhibiting characteristics of
these compositions are not discussed or claimed. Additional
manganese-containing colorants, frits, and ceramic pigments with no
discussed or claimed anticorrosive properties are identified in
U.S. Pat. No. 4,159,207 to Nuss, U.S. Pat. No. 3,832,205 to Lowery,
and U.S. Pat. No. 5,254,162 to Speer, et al., and German Patent
Nos. DE 4131 548 and DE 40 02 564, both to Speer, et al.
[0022] U.S. Pat. No. 4,469,521 to Salensky describes a
corrosion-inhibiting pigment formed by sintering manganomanganic
oxide (Mn.sub.3O.sub.4) with oxides of calcium, zinc, barium,
magnesium, or strontium.
[0023] U.S. Pat. No. 4,388,118 to Eppler describes a
corrosion-inhibiting black pigment formed by calcining calcium or
strontium oxides or carbonates with manganese oxides. The formed
calcium manganese oxide or strontium manganese oxide pigments have
very low oil absorption and high tint strength.
[0024] German Patents Nos. 26 42 049, 28 15 306, and 26 25 401 to
Hund, et al. describe the use of calcined
calcium/iron/aluminum/manganese oxides as corrosion-inhibiting
pigments.
[0025] Manganese oxides themselves have been described as being
constituents in corrosion-inhibiting formulations. For example,
U.S. Pat. Nos. 4,417,007 and 4,417,008 to Salensky, et al. as well
as Belgian Patent Nos. BE 893,677 to Chopra, et al. and BE 893,676
to Salensky, et al. describe manganomanganic oxide
(Mn.sub.3O.sub.4) as a constituent in a solvent-based paint
formulation comprised of resin binders and additional extenders,
fillers, and solvents. Manganese dioxide (MnO.sub.2) is also
described as an anticorrosive constituent within formulations in
French Patent No. 2,348,257 to Zatmann and German Patent No. DE 39
35 478 to Ortlepp.
[0026] U.S. Pat. No. 4,788,411 to Skinner describes a paint
composition described to prevent corrosion of welds. This
composition is described as being composed primarily of zinc dust,
with manganomanganic oxide (Mn.sub.3O.sub.4) and organic binder
included. The zinc pigment is described as being especially
important for corrosion protection.
[0027] To date, no truly effective replacements have been developed
for pigments based on CrVI or PbIV. Accordingly, the need remains
for improved corrosion-protective pigments composed of currently
unregulated and/or nontoxic materials which have an effectiveness,
ease of application, and performance comparable to current CrVI or
PbIV pigment formulations, and for methods of making and using the
same.
SUMMARY OF THE INVENTION
[0028] This need is met by the present invention which represents a
significant improvement in the formulation of non-toxic pigments
through the use of trivalent or tetravalent manganese. Although the
present invention is not limited to specific advantages or
functionality, it is noted that the trivalent and/or tetravalent
manganese pigments of the present invention have been demonstrated
with accelerated corrosion testing to retard corrosion to a higher
degree than prior art manganese pigments and other alternatives to
CrVI- or PbIV-based corrosion inhibiting pigments. These pigments
have been tested to inhibit corrosion to the same degree as zinc,
strontium, and lead chromate-based CrVI pigments, as well as red
lead or calcium plumbate Pb IV pigments. The raw materials are not
exotic, are relatively inexpensive, and do not require complicated
synthesis methods.
[0029] The present invention utilizes "valency stabilization" of
the trivalent or tetravalent manganese ion in the as-formed
pigments to achieve corrosion resistance comparable to the more
soluble chromate-based CrVI pigments. More specifically, in order
to achieve a high degree of corrosion resistance, a MnIII-based or
MnIV-based pigment must exhibit the following characteristics:
[0030] 1) A corrosion inhibiting pigment must contain a suitable
source of oxidizing species. These species quickly oxidize bare
metal and form a protective surface if bare metal is exposed in a
coating breach.
[0031] 2) A valence stabilizer for the trivalent or tetravalent
manganese ion is necessary to ensure that the ion will not be
reduced too quickly to the divalent state when released into
solution or in the coating. The importance of stabilizing the
manganese ion in its trivalent or tetravalent charge state was not
previously recognized as critical to the corrosion inhibiting
function of a pigment.
[0032] 3) The MnIII or MnIV pigment powder must be a "sparingly
soluble", "low solubility", or "insoluble" compound in water when
dispersed in its binder-carrier system. If the pigment is too
insoluble in a selected coating system that requires inhibitor
release, an insufficient amount of corrosion inhibitor will be
delivered to a flaw. A poorly formed, incomplete oxide layer
produced by a pigment of too low solubility for a given
binder-carrier system will not only fail to inhibit corrosion, but
can promote crevice corrosion and result in locally enhanced
corrosion rates.
[0033] The reservoir of oxidizing ions can be quickly flushed away
if the pigment is too soluble, and typical corrosion will begin.
Highly soluble pigments are also known to result in osmotic
blistering of paint films and coatings. Trivalent or tetravalent
manganese pigments that are too soluble can also be responsible for
osmotic blistering depending on the aqueous permeability the
carrier film.
[0034] It is difficult to place specific solubility values to these
optimum "sparingly soluble", "low solubility", or "insoluble"
pigment materials because there appear to be several variables
associated with what makes an optimum anticorrosive pigment
material (e.g., specific resin/binder system in which it is
placed). The particle size and particle shape has been observed to
noticeably affect the solubility of "low solubility" pigments such
as lead chromate (e.g., May and Kolthoff, J. Phys. & Colloid
Chem. 52: 836-54, 1948). The solubility of the candidate trivalent
or tetravalent manganese pigment must be matched to the hexavalent
chromium or tetravalent lead pigment that it is replacing (Table
1), such as zinc or strontium chromate, or calcium plumbate. If the
trivalent or tetravalent manganese pigment exhibits a solubility in
water of between about 1.times.10.sup.-4 and about
1.times.10.sup.-1 moles per liter of trivalent or tetravalent
manganese, then appreciable corrosion inhibition will be observed
in the binder systems that typically incorporate zinc or strontium
chromates (or calcium plumbate). Pigments that incorporate
stabilized trivalent or tetravalent manganese compounds that fall
outside of this particular range may also exhibit some corrosion
inhibition as zinc or strontium chromate (or calcium plumbate)
replacements. For example, pigments with solubilities as high as
1.times.10.sup.0 moles per liter or as low as 1.times.10.sup.-5
moles per liter of trivalent or tetravalent manganese at standard
temperature and pressure (about 25.degree. C. and about 760 Torr)
will exhibit some corrosion resistance in binder systems that
currently incorporate zinc or strontium chromate (or lead
plumbate), although not as great as those compounds which fall
within the optimum solubility range. A solubility range from
1.times.10.sup.-6 to 1.times.10.sup.-8 moles per liter trivalent or
tetravalent manganese is desirable for manganese pigments to
inhibit corrosion in binder systems where lead chromate pigments
are currently used. Pigments that incorporate trivalent or
tetravalent manganese that fall slightly outside of this range may
also inhibit corrosion as lead chromate replacements. For example,
pigments with solubilities as high as 1.times.10.sup.-5 moles per
liter or as low as 1.times.10.sup.-9 moles per liter of trivalent
or tetravalent manganese at standard temperature and pressure
(about 25.degree. C. and about 760 Torr) will exhibit some
corrosion resistance in binder systems that currently incorporate
lead chromate, although not as great as those compounds which fall
within the optimum solubility range. Lastly, any trivalent or
tetravalent manganese pigment that exhibits a solubility lower than
1.times.10.sup.-9, but higher than 1.times.10.sup.-17 (based on red
lead solubility) moles per liter of trivalent or tetravalent
manganese at standard temperature and pressure (about 25.degree. C.
and about 760 Torr) will exhibit some corrosion resistance in
binder systems that currently incorporate red lead. Under special
conditions (i.e., very carefully controlled particle sizes),
trivalent or tetravalent manganese compounds with solubilities as
high as 1.times.10.sup.-7 moles per liter trivalent or tetravalent
manganese can be used as red lead replacements. The solubility
characteristics of the trivalent or tetravalent manganese in the
pigment can be controlled through the use of valence stabilizer
materials that form compounds that fall within the desired
solubility ranges. A "controlled release" of trivalent or
tetravalent manganese can thus be achieved similar to the "timed
release" of hexavalent chromium or tetravalent lead in the
"state-of-the-art" systems.
1TABLE 1 Solubility Ranges for Trivalent and/or Tetravalent
Manganese Replacements for Hexavalent Chromium or Tetravalent Lead
Pigments Hexavalent Chromium Optimum Solubility Acceptable
Solubility or Tetravalent Lead Range (moles/L Range (moles/L
Pigment to be Replaced Mn.sup.+3 and/or Mn.sup.+4) Mn.sup.+3 and/or
Mn.sup.+4) Zinc Chromates 1 .times. 10.sup.-1 (upper) 1 .times.
10.sup.0 (upper) (including basic forms) to to Strontium Chromates
1 .times. 10.sup.-4 (lower) 1 .times. 10.sup.-5 (lower) Calcium
Plumbate Lead Chromates 1 .times. 10.sup.-6 (upper) 1 .times.
10.sup.-5 (upper) (including basic forms) to to Lead
Molybdate-Chromate 1 .times. 10.sup.-8 (lower) 1 .times. 10.sup.-9
(lower) Lead Silicochromate Red Lead 1 .times. 10.sup.-9 (upper) 1
.times. 10.sup.-7 (upper) to to 1 .times. 10.sup.-17 (lower) 1
.times. 10.sup.-17 (lower)
[0035] 4) The "valence stabilizer" optionally helps establish an
electrostatic barrier layer around the cation-stabilizer compound
in aqueous solutions. The nature and character of the electrostatic
double-layer surrounding the cation-stabilizer compound may be
controlled and modified by careful selection of stabilizer species.
In general, the electrostatic double layer formed acts to protect
the cation from premature reaction with hydronium, hydroxide, and
other ions in solution. The formation of electrostatic barrier
layers also helps to impede the passage of corrosive ions through
the binder phase to the metallic surface.
[0036] 5) The trivalent or tetravalent manganese pigment material
may also exhibit ion exchange behavior towards corrosion promoting
ions, particularly alkali species. This optional consideration can
be important because alkali ions are aggressive aqueous corrosion
enhancers in alloys which contain metals such as aluminum,
magnesium, or zinc.
[0037] 6) The manganese/valence stabilizer complex can optionally
exhibit a color change between the trivalent or tetravalent and
divalent manganese oxidation states. This color change can act as a
metric to determine when the "throwing power" associated with the
pigments is no longer available, and when the paint system in which
it is contained needs to be replaced. For this reason, it is also
optionally important that the color of these pigments that exhibit
a color change between divalent and trivalent or tetravalent
oxidation states that is light-fast (i.e., not changed by strong
light).
[0038] The effectiveness of an oxidizing species is a function of
its individual oxidation-reduction potential, and more highly
oxidized species exhibit greater corrosion protection, although
lower stability. A stabilizer is necessary to provide a timed
release of the inhibitor ion, as well as being needed to ensure
that the oxidative strength will not be reduced too rapidly. Thus,
a valence stabilizer is required for the trivalent or tetravalent
manganese ion because of its reactivity and to produce controlled
trivalent or tetravalent manganese solubilities. The corrosion
resistance of a number of aluminum alloys as tested using both ASTM
B-117 and ASTM G-85 has been enhanced through the use of stabilized
trivalent and/or tetravalent manganese pigments. Not only do these
optimized pigments retard corrosion to a higher degree than other
prior art manganese pigments, but their corrosion resistance is
comparable to that of hexavalent chromium or tetravalent lead
systems.
[0039] In one aspect, the invention comprises a mechanistic and
chemical approach to the production of corrosion-inhibiting
pigments using trivalent or tetravalent manganese. This approach
uses stabilizer materials which form compounds with trivalent or
tetravalent manganese that match the observed solubilities of
hexavalent chromium or tetravalent lead pigments currently in use
(see Table 1). The solubility ranges reported provide a release of
trivalent or tetravalent manganese at a rate slow enough that most
binder systems will provide protection for an extended period of
time and fast enough to inhibit corrosion during conventional
accelerated corrosion testing methods such as ASTM B-117 and G-85.
Compounds that fall slightly outside of the solubility ranges shown
in Table 1 may also provide some corrosion-inhibiting activity
under certain conditions and binder systems. However, pigment
compounds with aqueous solubilities far outside of the target
ranges are likely to be inefficient corrosion inhibitors.
Solubility control can be achieved using organic or inorganic
stabilizer materials.
[0040] In an optional aspect, the invention is the achievement of
corrosion-resistant pigments using trivalent or tetravalent
manganese by the use of stabilizer materials which form compounds
that exhibit electrostatic dipoles to form electrostatic barrier
layers composed of ions such as hydronium (H.sub.3O.sup.+) or
hydroxide (OH.sup.-) in the presence of water. The formation of
these electrostatic barrier layers through the use of stabilizer
materials can be achieved using organic or inorganic materials.
[0041] In another optional aspect, the invention is the achievement
of corrosion-resistant pigments using trivalent or tetravalent
manganese by the use of stabilizer materials which form compounds
that exhibit ion exchange behavior towards alkali ions. The
formation of this ion exchange behavior can be achieved through the
use of organic or inorganic materials.
[0042] In yet another optional aspect, the decomposition
temperature of the trivalent or tetravalent manganese/valence
stabilizer complex upon which the pigment is based should be above
100.degree. C. In addition, the melting temperature of the complex
is typically above 50.degree. C., although lower-melting complexes
may have some applications.
[0043] In still another optional aspect, the manganese/valence
stabilizer complex upon which the pigment is based should exhibit a
color change between the trivalent or tetravalent and divalent
oxidation states. This allows for a visual metric of when the
pigment has lost its "throwing power", and the binder system within
which it is contained must be replaced. Therefore, it is desirable
that the color of these pigments be light-fast (unchanged by
exposure to strong light).
[0044] These MnIII and MnIV compounds represent a substantial
performance improvement over prior art related to pigment
alternatives used to replace CrVI-based and PbIV-based corrosion
inhibiting pigments. They also provide a capability to tailor the
corrosion inhibiting pigment to the carrier system. This allows
current binder/resin systems used for chromates or plumbates to be
used for MnIII- or MnIV-based systems without modification.
Likewise, new binder/carrier/resin systems with improved physical
properties can be developed without the restriction of
compatibility with zinc, strontium, or lead chromate; or plumbate
pigments.
[0045] The raw materials needed for the solutions used to form
these coatings are relatively inexpensive. The pigments do not use
exotic materials or require complicated synthesis methods.
[0046] Accordingly, it is an object of the present invention to
provide non-toxic, corrosion-protective pigments based on trivalent
or tetravalent manganese and for methods of making and using the
same. These and other objects and advantages of the present
invention will be more fully understood from the following detailed
description of the invention. It is noted that the scope of the
claims is defined by the recitations therein and not by the
specific discussion of features and advantages set forth in the
present description.
DETAILED DESCRIPTION OF THE INVENTION
[0047] A. Starting Materials
[0048] Four general starting materials are used for the preparation
of trivalent or tetravalent manganese corrosion-inhibiting
pigments. These include a manganese source, an oxidation source (if
the precursor is a divalent manganese salt), a valence stabilizer
source, and optional additional solubility control agents.
[0049] 1) Manganese Source
[0050] Manganese is a nontoxic, non-regulated replacement metal for
chromium or lead that exhibits more than one oxidation state (MnII,
MnIII, and MnIV). The oxidation reduction potential for MnIII-MnII
is comparable to that of the CrVI-CrIII couple, and the
oxidation-reduction potential for MnIV-MnIII is comparable to the
PbIV-PbII couple. The ionic radii of MnIII (61 pm) and MnIV (54 pm)
are slightly larger than the CrVI ion (44 pm), and they will have a
correspondingly lower charge density (electrostatic field) per ion
as compared to hexavalent chromium. Conversely, both MnIII and MnIV
are smaller than PbIV (78 pm), and have a higher charge density
(electrostatic field) per ion compared to tetravalent lead. These
factors are important in the selection and design of trivalent or
tetravalent manganese compounds that match or exceed the
performance of hexavalent chromium or tetravalent lead
pigments.
[0051] Unlike most other high valence metal (HVM) systems,
trivalent and/or tetravalent manganese ions exhibit remarkable
stability under many environmental conditions. The numerous
examples of manganese minerals that contain MnIII or MnIV are
evidence of this stability (see Table 2 below). Trivalent or
tetravalent manganese-containing minerals could conceptually be
used as corrosion-inhibiting pigments. (However, natural impurities
contained therein would alter the compositions so that the pigment
materials would exhibit altered solubility characteristics.) The
trivalent or tetravalent manganese minerals shown in Table 2 could
be used as precursors for the production of anticorrosive manganese
pigments for lead chromate or red lead replacements.
2TABLE 2 Naturally-Occurring Trivalent and/or Tetravalent
Manganese-Containing Minerals Useful as Feedstock for Anticorrosive
Manganese Pigment Production Manganese Approximate Valence Crystal
Mineral Composition State(s) Structure Pyrolusite MnO.sub.2 +4
Tetragonal Hausmannite Mn.sub.3O.sub.4 +3/+2 Tetragonal Manganite
MnO(OH) +3 Tetragonal Ramsdellite MnO.sub.2 +4 Orthorhombic
Bixbyite Mn.sub.2O.sub.3 +3 Cubic Groutite MnO(OH) +3 Orthorhombic
Feitknechite MnO(OH) +3 Tetragonal Akhtenskite MnO.sub.2 +4
Hexagonal Buserite MnO.sub.2 +4 Unknown Nsutite Mn(O,OH).sub.2
+4/+3 Hexagonal Hetacrolite ZnMn.sub.2O.sub.4 +3 Tetragonal
Marokite CaMn.sub.2O.sub.4 +3 Orthorhombic Hydro-
HZnMn.sub.2-xO.sub.4 +3/+2 Tetragonal hetaerolite Braunite
Mn.sub.7SiO.sub.12 +3/+2 Tetragonal Psilomelane
(Ba,H.sub.2O).sub.2Mn.sub.5O.sub.10 +4/+3 Monoclinic (aka Roman-
echite) Crypt- KMn.sub.8O.sub.16 +4/+3 Monoclinic or omelane
Tetragonal Manjiroite (K,Na)Mn.sub.8O.sub.16 +4/+3 Tetragonal
Lithiophorite (Al.Li)MnO.sub.2(OH).sub.2 +4/+3 Hexagonal Chal-
(Zn,Fe,Mn)Mn.sub.3O.sub.7 +4 Rhombohedral cophanite Hollandite
(Ba,K,Na)Mn.sub.8(O,OH).sub.16 +4/+3 Unknown Woodruffite
(Zn,Mn)Mn.sub.3O.sub.7 +4 Tetragonal Neltnerite
CaMn.sub.6SiO.sub.12 +3 Tetragonal Birnessite
Na.sub.4Mn.sub.14O.sub.27 +4/+3 Hexagonal Asbolane
(Ni,Co).sub.xMn(O,OH).sub.4 +4/+3 Hexagonal Todorokite
(K,Ca,Na)(Mn,Al,Mg).sub.6O.sub.12 +4/+3 Monoclinic Vernadite
(Mn,Fe,Ca,Na)(O,OH).sub.2 +4/+3 Hexagonal
[0052] a) Manganese Sources for "Sparingly Soluble" Pigments
[0053] Zinc and strontium chromates, as well as calcium plumbate,
are "sparingly soluble" in water, and are typically formed via
precipitation from a liquid media (i.e., water), with subsequent
particle sizing and powder processing. Trivalent or tetravalent
manganese pigments to be used for the same applications as zinc and
strontium chromates, or calcium plumbate, are produced in a similar
fashion. This is because the higher solubility requirements
(1.times.10.sup.-1 to 1.times.10.sup.-4 moles/liter inhibitor ion)
for these pigments necessitate much higher release rates of MnIII
or MnIV than can typically be achieved by calcined or "fired"
materials. MnIII or MnIV compounds that can achieve high
solubilities and release rates require special valence stabilizer
and/or solubility control agents. The easiest preparative method
for these constituents is via precipitation processes.
[0054] Manganese precursors for "sparingly soluble" pigments can be
nearly any water, alcohol, or hydrocarbon soluble manganese
compound in which the manganese is in the divalent, trivalent,
tetravalent, or heptavalent oxidation state. Water-soluble
precursors are typically used. Inorganic divalent manganese
precursor compounds include, but are not limited to, manganese
nitrate, manganese sulfate, manganese perchlorate, manganese
chloride, manganese fluoride, manganese bromide, manganese iodide,
manganese bromate, manganese chlorate, and complex fluorides such
as manganese fluosilicate, manganese fluotitanate, manganese
fluozirconate, manganese fluoborate, and manganese fluoaluminate.
Organometallic divalent manganese precursor compounds include, but
are not limited to, manganese formate, manganese acetate, manganese
propionate, manganese butyrate, manganese valerate, manganese
benzoate, manganese glycolate, manganese lactate, manganese
tartronate, manganese malate, manganese tartrate, manganese
citrate, manganese benzenesulfonate, manganese thiocyanate, and
manganese acetylacetonate.
[0055] The manganese precursor for "sparingly soluble" pigments may
also be a compound with manganese already in the trivalent or
tetravalent oxidation state. A representative example is manganese
III acetylacetonate. The manganese precursor for "sparingly
soluble" pigments may be a compound with the manganese in the
heptavalent oxidation state (permanganates). Heptavalent manganese
precursors include, but are not limited to: potassium permanganate,
sodium permanganate, lithium permanganate, ammonium permanganate,
magnesium permanganate, calcium permanganate, strontium
permanganate, barium permanganate, zinc permanganate, ferric
permanganate, nickel permanganate, copper permanganate, cobalt
permanganate, cerium permanganate, lanthanum permanganate, yttrium
permanganate, and aluminum permanganate.
[0056] b) Manganese Sources for "Low Solubility" or "Insoluble"
Pigments
[0057] Lead chromates are typically formed via precipitation from
aqueous solution, while red lead pigments are produced by firing
PbII oxide (PbO) in an oxidizing environment at approximately
400.degree. C. Trivalent or tetravalent manganese compounds to be
used as lead chromate or red lead replacements can be formed in two
ways: 1) precipitating a manganese compound from a liquid medium
and then firing or calcining the resultant precipitate; or 2)
calcining or firing a manganese-containing compound or mixture
using insoluble precursors. The commonality between these two
options is firing, calcining, or otherwise heating a
manganese-containing compound or mixture. The only manganese
compounds suitable as replacements for lead chromate or red lead
pigments (<1.times.10.sup.-5 moles/liter inhibitor ion) are
those produced by calcining or heating manganese compounds with or
without other additives.
[0058] Soluble manganese sources for precipitation prior to
calcining, firing, or otherwise heating are similar to those
described above for "sparingly soluble" pigments. Insoluble
manganese-containing compounds useful as precursors include MnII,
MnIII, MnIV, and some MnIV compounds. Insoluble divalent manganese
compounds useful as precursors include, but are not limited to:
manganese oxide (manganosite), manganese hydroxide (pyrochroite),
manganese carbonate (rhodochrosite), manganese silicate (rhodonite,
tephroite, manganhumite, or manganjustite), manganese sulfide
(alabandite or hauerite), manganese phosphate (reddingite or
hureaulite), manganese oxalate, and manganese borate. Insoluble
trivalent manganese or tetravalent manganese compounds suitable as
precursors include manganese dioxide (MnO.sub.2), manganomanganic
oxide (Mn.sub.3O.sub.4), manganese sesquioxide (Mn.sub.2O.sub.3),
lithiated manganese spinel (LiMn.sub.2O.sub.4), and manganese III
hydroxide (MnOOH). The MnIII and MnIV containing minerals described
in Table 1 are also useful insoluble trivalent and tetravalent
manganese precursors.
[0059] MnIII and MnIV are capable of providing corrosion protection
at a distance to a metal surface in the presence of coating flaws
such as scrapes, scratches, and holes because of their throwing
power. The solubility of the MnIII or MnIV compound needs to be
tailored to suit the needs of the protection system and must be
neither too high, nor too low in that system. The protective system
includes the binder phase, assorted modifiers, and under- and
over-coatings. The system needs to be performance matched to its
intended usage environment. Timely release and throwing power of
the inhibitor are critical to protective performance, but
controlled tailoring of these has not been taught in prior art.
Likewise, the body of systematic chemistry data required to control
these properties has not been readily available in a form useful to
help design coatings. The present invention outlines how to
stabilize MnIII and MnIV with a variety of materials so the MnIII
and MnIV may be adapted to a multitude of pigment applications with
specific compatibility requirements.
[0060] 2) Oxidation Source
[0061] If MnIII and/or MnIV pigment compounds are produced via
precipitation, an oxidizing species will typically be included in
the synthesis solution if divalent manganese compounds are used as
precursors for MnIII and MnIV. Otherwise, a post-precipitation
oxidation step will be required. Additional amounts of oxidizer may
be added to help control and maintain a desired amount of
MnIII/MnIV in the pigment solution by reoxidizing MnIII/MnIV that
has become reduced. The trivalent manganese ion is an exceptionally
good oxidizing species with an oxidation-reduction potential of
+1.49 V at a pH of 0 for the MnIII-MnII couple in water, and the
tetravalent manganese ion is an even stronger oxidizing species,
with a redox potential of +1.65 V under similar conditions. Strong
oxidizers are required because of the high potential of their redox
reaction. The oxidizers may be gases, liquids, or solids. Solid
oxidizers are typically used for this application due to ease of
handling and reagent measurement. Other starting materials
(manganese source and stabilizer source) will also frequently be
solids. Liquid oxidizers may be used, but handling and accurate
process metering have proven difficult. Gaseous oxidizers may be
the most cost effective and chemically efficient on a large scale,
but are also the most problematic due to handling and venting
concerns.
[0062] Oxidizers suited for the purpose of producing and
maintaining the manganese ion in the trivalent or tetravalent
charge state include but are not restricted to peroxides and peroxo
compounds (including superoxides, persulfates, perborates,
pernitrates, perphosphates, percarbonates, persilicates,
peraluminates, pertitanates, perzirconates, permolybdates,
pertungstates, pervanadates, and organic peroxyacid derivatives),
ozone, hypochlorites, chlorates, perchlorates, nitrates, nitrites,
vanadates, iodates, hypobromites, chlorites, bromates,
permanganates, periodates, and dissolved gases such as oxygen,
fluorine, or chlorine. Inorganic and organic derivatives of these
compounds may be used. Typical oxidizers for this use are
peroxides, persulfates, perbenzoates, periodates, bromates,
hypochlorites, gaseous dissolved oxygen, and even the oxygen
content of air. In general, any inorganic, organic, or combination
species with an oxidation potential of +1.0 V or greater (at a pH
of 1) will be capable of oxidizing divalent manganese to the
trivalent or tetravalent oxidation state.
[0063] Oxidized manganese may also be produced in solution by
electrolytic oxidation. However, this approach may not be
economically feasible due to the energy costs associated with
electrolytic oxidation. Chemical oxidation, such as that described
above, currently offers the best-value approach for oxidizing
manganese to the trivalent or tetravalent state.
[0064] It is also possible to produce a divalent manganese/valence
stabilizer complex, and then apply an oxidizer to oxidize divalent
manganese to trivalent or tetravalent manganese. This, however, is
less typical because the percentage of trivalent or tetravalent
manganese will decrease from the outside to the interior of the
pigment particle.
[0065] Oxygen (including the oxygen content of air) is the most
useful oxidizer source for the production of "low solubility" or
"insoluble" trivalent or tetravalent manganese pigment compounds
via calcining, firing, or otherwise heating processes. The control
of temperature, partial pressure of oxygen, flowrate, and even
particle size allows the oxidation state of the manganese in the
sintered particle to be divalent, trivalent, or tetravalent. Other
oxidizing gasses such as NO.sub.x, SO.sub.x, chlorine, fluorine, or
ozone can also be used, but these are less desirable due to their
environmental impact.
[0066] 3) Valence Stabilizers
[0067] Manganese is effective as an oxidative corrosion inhibitor
if it can be supplied in sufficient quantities in the trivalent
and/or tetravalent charge-state when brought into contact with
unprotected bare metal. Corrosion resistance comparable to that of
CrVI or PbIV can be achieved by the use of MnIII and/or MnIV
oxidizer ions in pigment compounds. Valence stabilizers are
materials that, when assembled, modify the rate of reduction and
the solubility of the MnIII and/or MnIV ions. Valence stabilization
has not been previously recognized as an important consideration in
the development of effective corrosion inhibiting pigments.
Stabilization helps avoid reduction and premature conversion of the
ion to the divalent charge-state during compound formation, carrier
incorporation, application, and exposure to a corrosive
environment. Stabilizers control solubility, mobility, ion
exchange, binder compatibility, and the degree of surface wetting.
The exact solubility of this compound may be modified by species
released into solution by the dissolving metal surface or by the
subsequent addition of solubility control agents. A variety of
inorganic and organic stabilizers are available that can serve to
control solubility. The stabilizer may also act as an ion-exchange
host and/or trap for alkali or halide ions in solution.
[0068] Valence stabilization is necessary for MnIII and MnIV due to
the reactivity of these ions with water. Unlike MnII, which can
readily be solubilized in water, MnIII and MnIV ions rapidly react
with water, producing elemental oxygen. Valence stabilization is
particularly useful for the more soluble MnIII and MnIV compounds
(i.e., >1.times.10.sup.-5 moles/liter of inhibitor ion) where
more rapid release rates of these ions are necessary. For example,
manganese dioxide (MnO.sub.2) is reported to exhibit a solubility
in water between 2.4.times.10.sup.-5 and 4.0.times.10.sup.-7
moles/liter Mn.sup.+4, depending upon pH (Swain, et al., Anal.
Chem. 47(7): 1135-7, 1975 and Savenko, Geokhimiya (3) pp. 416-9,
1985). Similarly, manganese sesquioxide (Mn.sub.2O.sub.3) is
reported to exhibit a solubility in water between
3.3.times.10.sup.-8 and 5.1.times.10.sup.-9 moles/liter Mn.sup.+3,
depending upon temperature (Ampelogova, et al., Radiokhimiya 31(4):
160-5, 1989). For these low solubility compounds, oxygen (O) is a
satisfactory "valence stabilizer" to achieve the desired
solubilities and release rates. Specialized valence stabilizers are
necessary for MnIII and MnIV compounds of solubilities higher than
1.times.10.sup.-5 moles/liter Mn.sup.+3 or Mn.sup.+4.
[0069] The need for "valence stabilization" of trivalent or
tetravalent manganese for corrosion inhibition has only been
indirectly noted in the general corrosion literature as a
synergistic enhancement. Corrosion inhibition behavior of
nitrogen-containing organics such as aniline or pyridine has been
reported to be enhanced with the addition of manganese. The exact
nature of this "synergistic enhancement" has never been adequately
explained. These "synergistic" mixtures of nitrogen-containing
organics and manganese have also been described as being
"oxygen-scavengers", and the organics are frequently observed to
"chemisorb" onto the substrate piece being protected.
[0070] This enhancement can be explained by the "valence
stabilization" model of corrosion inhibition by trivalent or
tetravalent manganese outlined here. Nitrogen-containing organics
and manganese result in the formation of an organometallic complex
where the central manganese ion can be stabilized in a higher
oxidation state. The observed "oxygen-scavenging" phenomenon
associated with dissolved oxygen in aqueous solutions is easily
explained by the oxidation of stabilized divalent manganese to the
trivalent or tetravalent state. "Sparingly soluble" MnIII or MnIV
complexes containing these organics are responsible for the
corrosion inhibiting activity, and these organics will appear to be
"adsorbed" or "chemisorbed" from solution onto the metal piece
being protected due to precipitation.
[0071] The key to providing a useful source of trivalent or
tetravalent manganese at a metal surface is the creation of a
compound in which the MnIII or MnIV ion is shielded from premature
reduction during and after pigment formation. The formation of
pigments with the proper release rate of MnIII or MnIV ions is
problematic because of the instability of MnIII and MnIV in
solution. A valence stabilizer must assemble around MnIII or MnIV
to form a compound in order to produce the active
corrosion-inhibiting component in a pigment. It is difficult to
place specific solubility values to these optimum sparingly soluble
pigments because of the wide range of binder systems in which
corrosion-inhibiting pigments are used.
[0072] In order to replace the zinc chromates, strontium chromate,
or calcium plumbate pigments, a MnIII- or MnIV-stabilized compound
with a solubility in water of between about 1.times.10.sup.-4 and
about 1.times.10.sup.-1 moles per liter of trivalent or tetravalent
manganese should exhibit appreciable corrosion inhibition when used
as a primer pigment. This solubility range provides a release of
trivalent or tetravalent manganese at a rate slow enough that
protection will be provided for an extended period of time and fast
enough to inhibit corrosion during conventional accelerated
corrosion testing methods such as ASTM B-117 and G-85 for coatings
that contain these pigments. Manganese compounds that fall outside
of this particular solubility range may exhibit a small degree of
corrosion inhibition in the binder systems that currently use the
zinc or strontium chromate pigments. For example, compositions with
solubilities as high as 1.times.10.sup.0 moles per liter or as low
as 1.times.10.sup.-5 moles per liter of trivalent or tetravalent
manganese will exhibit some corrosion resistance, although they
will not be as effective as those compounds within the optimum
solubility range. A common MnIII compound (MnIII acetylacetonate)
is too soluble to provide effective corrosion inhibition if
incorporated into a binder system such as a paint. Other compounds,
such as Mn.sub.3O.sub.4 as described in the prior art, will not
serve as effective corrosion inhibiting pigments in the binder
systems that currently use the zinc or strontium chromate pigments
because they are too insoluble.
[0073] The needed solubility will be strongly dependent on the net
aqueous solubility of overlying paints and coatings and their usage
environment. For example, solubility tailoring would be useful in a
situation where a protected substrate is suddenly immersed in
seawater, or where a rubber sealant allows only limited water
penetration. Adequate corrosion protection could be achieved
through the formation of a trivalent or tetravalent manganese
pigment compound that exhibits a higher solubility in water (e.g.,
1.times.10.sup.0 to 1.times.10.sup.-3 moles per liter MnIII or
MnIV). A rapid release of protective trivalent or tetravalent
manganese ions would happen at the expense of depleting the
manganese quickly from the coating. Trivalent or tetravalent
manganese pigments of lower solubilities (e.g., 5.times.10.sup.-5
to 1.times.10.sup.-3 moles per liter MnIII or MnIV) may also be
useful in some situations (e.g., as paints in nearly pure
deoxygenated water). The number and range of compound solubilities
offered by valence stabilized MnIII and MnIV compounds allows the
development of protective coating systems with broad performance
and application ranges. This feature is not presently available
even for CrVI based corrosion inhibiting pigments.
[0074] Any material in the synthesis bath which complexes with
trivalent or tetravalent manganese (whether inorganic or organic)
and which results in the formation of a MnIII- or MnIV-containing
compound that exhibits solubilities within or near this solubility
range can serve as a valence stabilizer for trivalent or
tetravalent manganese. The assembly of a protective shell around
the highly charged MnIII or MnIV and its associated oxygen and
hydroxyl species can help control the rate at which the manganese
is reduced and its oxygen is released. Proper selection of
materials for forming the protective shell will allow solubility
tailoring of the entire assembly to its intended application
environment. Valence stabilizers described above may need some type
of additional solubility control to optimize the performance of the
trivalent or tetravalent manganese-valence stabilizer compound.
Additional solubility control agents may be in the form of
inorganic or organic compounds. Their use is optional rather than a
requirement for effective valence stabilization and solubility
control.
[0075] Trivalent or tetravalent manganese-containing compounds that
are useful as replacements for lead chromate or red lead pigments
require lower solubilities. A typical formula for a red lead paint
is:
3 Red lead (Pb.sub.3O.sub.4) 80 wt. Percent Linseed oil 18 wt.
Percent Turpentine and liquid drier 2 wt. Percent
[0076] The majority of this paint system is pigment. If the pigment
in this paint system exhibited excessive solubilities for this
specific application, the coating would quickly be exhausted,
leaving limited protection for the underlying metal.
[0077] An optimum solubility range from 1.times.10.sup.-6 to
1.times.10.sup.-8 moles per liter trivalent or tetravalent
manganese is desirable for manganese pigments to inhibit corrosion
in the binder systems that lead chromate pigments currently are
used in. Pigments that incorporate trivalent or tetravalent
manganese that fall slightly outside of this range may also inhibit
corrosion as lead chromate replacements. For example, pigments with
solubilities as high as 1.times.10.sup.-5 moles per liter or as low
as 1.times.10.sup.-9 moles per liter of trivalent or tetravalent
manganese at standard temperature and pressure (about 25.degree. C.
and about 760 Torr) will exhibit some corrosion resistance in
binder systems that currently incorporate lead chromate, although
not as great as those compounds which fall within the optimum
solubility range.
[0078] Any trivalent or tetravalent manganese pigment that exhibits
a solubility lower than 1.times.10.sup.-9 moles per liter of
trivalent or tetravalent manganese at standard temperature and
pressure (about 25.degree. C. and about 760 Torr) will exhibit some
corrosion resistance in binder systems that currently incorporate
red lead. Under special conditions (i.e., very carefully controlled
particle sizes), trivalent or tetravalent manganese compounds with
solubilities as high as 1.times.10.sup.-7 moles per liter trivalent
or tetravalent manganese can be used as red lead replacements.
[0079] As with the more soluble MnIII and MnIV compounds used as
zinc or strontium chromate replacements, changes in pigment
solubility can be achieved through the use of additional solubility
control agents.
[0080] Several variables are associated with making optimized
pigments. If the pigment is too insoluble for the specific
application, then insufficient trivalent or tetravalent manganese
is available to inhibit corrosion. Low solubility compounds that do
not provide a sufficient amount of oxidation quickly enough to a
coating breach may produce an incomplete oxide layer and thus an
ineffective barrier film. If the manganese pigment is too soluble,
it will be washed away quickly, and an incomplete thin oxide film
will form that will not provide long-term corrosion protection, or
osmotic blistering of the paint system may result. The formation of
spotty or patchy oxides can promote localized crevice corrosion and
can result in enhanced corrosion rates at the breach.
[0081] The traditional chromate pigments are used not only in alkyd
resin systems (e.g., DoD-P-15328D Wash Primers), but also in
acrylic systems (e.g., MIL-P-28577B Water-Borne Acrylic Primers),
and even in sulfonated rubber sealants (e.g., MIL-PRF-81733D
Sealing and Coating Compound). Tetravalent lead pigments are
typically used in either oil-based (i.e., linseed oil) paint
systems, although some are used in alkyd resin coatings.
Fortunately, it is possible to tailor the MnIII and/or MnIV valence
stabilizer compound pigment systems themselves to specific
binder/solvent systems using solubility (cohesion) parameters.
Solubility parameters define how well an inorganic or
organometallic complex will disperse in a given resin/binder
system. This represents a radical departure from traditional paint
systems, in which the paint systems are configured to specific
pigments.
[0082] The formation of an electrostatic double layer can be
important for the effectiveness of a corrosion inhibitor once it is
released into solution during corrosion. There are differences in
anodic and cathodic polarization, solubility, and the saturated pH
of aqueous solutions of various chromate or plumbate pigments. The
formation of an electrostatic double layer around the pigment while
in its carrier film will not be as important as when the species is
in solution. For this reason, the development of an electrostatic
double layer around the pigment is an optional consideration. For
example, zinc chromate pigment-filled paint does not exhibit
electrochemical inhibiting behavior. The carrier film typically
behaves as a water impermeable barrier and will muffle the polar
character of the pigment. The hexavalent chromium pigments
SrCrO.sub.4 and ZnCrO.sub.4 have very small barrier layers
associated with them, but they are effective as
corrosion-inhibiting pigments. Optimized solubility for MnIII- or
MnIV-valence stabilizer compounds alone can result in corrosion
resistance comparable to the state-of-the-art chromium pigments.
The degree of polarization exhibited by the MnIII or MnIV ions will
be less than the CrVI ion because of their larger ionic radius and
lower charge-state, and they will not be as efficient in forming
electrostatic double layers in aqueous solution. The valence
stabilization of trivalent or tetravalent manganese should be
optimized to achieve the highest degree of efficiency in both
solubility control and polar character, in order to further enhance
the corrosion resistance.
[0083] Conversely, because both the MnIII and MnIV ions are smaller
than the PbIV ion, the degree of polarization exhibited by these
ions will be greater than PbIV, and they will be more effective in
forming electrostatic double layers in aqueous solution. In order
to replace PbIV pigments, a lower degree of valence stabilization
is therefore acceptable.
[0084] The nature and character of the "electrostatic double layer"
surrounding the trivalent or tetravalent manganese/valence
stabilizer compound may be controlled and modified by careful
selection of organic or inorganic stabilizers. Characteristics such
as the electrical dipole moment and the shape/conformation (for
steric effects) of the stabilizer were found to influence the
performance of the corrosion-inhibiting pigment. These stabilizer
ions establish a protective electrostatic shell around the
cation-stabilizer compound and gather additional layers of ions
such as hydronium (H.sub.3O.sup.+) or hydroxide (OH.sup.-) about
them. The size of the electrostatic double layer is a function of
the electrostatic potential at the compound surface and is
inversely proportional to the ionic strength of the surrounding
solution. An electrostatic double layer will likely form in aqueous
solution for compounds that can carry a charge, have a natural
electrostatic dipole, or can have an induced dipole. However, these
compounds do not normally act as corrosion inhibitors because they
have not been optimized for that purpose.
[0085] The melting point and decomposition temperature of the
pigment material are important. Trivalent or tetravalent
manganese-valence stabilizer compounds that decompose below about
100.degree. C. limit both their useful lifetimes and range of use.
The melting temperature should be above about 50.degree. C. to
ensure that the liquid phase does not form during normal handling
procedures. An additive may be needed for pigments with melting
temperatures below about 50.degree. C. Inert solid addendum
materials need not have any inherent corrosion-inhibiting
capability and are used to provide a base (support) that the
pigment can absorb on or into. Oxides, phosphates, borates,
silicates, and polymers are examples of support compounds that can
be used. Low melting temperature pigments (below about 50.degree.
C.) can be used, but they require handling and processing different
from higher melting temperature pigments. Liquid-phase corrosion
inhibitors based on MnIII, MnIV, and CrVI pigments have been
demonstrated to provide excellent performance as corrosion
inhibitors in primer paint systems.
[0086] The corrosion-inhibiting pigments of the present invention
can optionally exhibit a color change between oxidized species and
divalent species. The implications of these color changes from an
applications standpoint are significant. Color changes in the
pigment material in use can be used as a metric to determine when
the pigment no longer exhibits corrosion-inhibiting action as a
result of depleting the oxidized ion. Changes in hue of the pigment
can be used to determine how much service life remains for that
pigment in terms of corrosion-inhibiting capacity. Valence based
color change is an attribute that conventional chromate or plumbate
pigments do not exhibit. The color change associated with their
redox reaction of chromate or plumbate pigments is insignificant as
the pigments are reduced and "depleted" of their
corrosion-inhibitive capability. Thus, trivalent or tetravalent
manganese/valence stabilizer combinations that exhibit these color
changes are superior to chromium or lead in terms of providing an
easily measured, easily observed metric to gauge remaining service
life of the pigment. However, this color change should not be
initiated by exposure to strong light. Light-fast pigments are
therefore desirable for these indicator pigments.
[0087] The incorporation of the valence stabilizer (inorganic or
organic) may optionally result in the formation of a MnIII- or
MnIV-valence stabilizer compound that also exhibits ion exchange
behavior towards alkali ions. This is not a requirement of the
MnIII- or MnIV-valence stabilizer compound, and pigments that do
not exhibit this phenomenon have been successfully demonstrated to
inhibit corrosive attack. However, it is a desirable characteristic
for enhanced corrosion resistance. Existing CrVI-based or
PbIV-based pigment systems do not exhibit this behavior to any
significant degree.
[0088] The design of suitable MnIII- or MnIV-valence stabilizer
compounds allows typical and less typical stabilizers to be
identified. The general classes of compounds described below
represent only a first approximation of whether a specific
coordination compound will provide favorable or unfavorable
properties in a MnIII- or MnIV-valence stabilizer compound.
Property tailoring can also take place through selection of
specific anions or cations bound to the MnIII- or MnIV-valence
stabilizer coordination compound. The "physiology" of inorganic
stabilizers is simple because of the limited number of atoms and
structural arrangements involved in their formation. The
"physiology" of organic stabilizers is not as simple. An
organically stabilized manganese compound may have one or more
organic ligands that may have one or more bonding sites that can
interact with the MnIII or MnIV ion/oxide cluster. The bonding
groups can be the same or different atoms or functional groups on
an individual or a variety of ligands. An organic stabilizer ligand
can be modified in an unlimited number of ways to tailor its
physical behavior with respect to such properties as chemical
reactivity, solubility, electrostatic and polar character, and
functional behavior.
[0089] It is possible to fine tune the electronic and structural
characteristics of a MnIII- or MnIV-valence stabilizer compound
further via substituent groups on the coordinating ligand, and/or
by the selection of cations or anions to complete the charge
balance of the MnIII- or MnIV-valence stabilizer compound. For
example, some substituent groups have large dipole moments
associated with them, which will increase the electrostatic barrier
layers associated with the manganese/valence stabilizer complexes.
These include: ketones (.dbd.C.dbd.O), thioketones (.dbd.C.dbd.S),
amides (--C[.dbd.O]--NR.sub.2), thioamides (--C[.dbd.S]--NR.sub.2),
nitrites or cyano groups, (--CN), isocyanides (--NC), nitroso
groups (--N.dbd.O), thionitroso groups (--N.dbd.S), nitro groups
(--NO.sub.2), azido groups (--N.sub.3), cyanamide or cyanonitrene
groups (.dbd.N--CN), cyanate groups (--O--CN), isocyanate groups
(--N--C.dbd.O), thiocyanate groups (--S--CN), isothiocyanate groups
(--N.dbd.C.dbd.S), nitrosamine groups (.dbd.N--N.dbd.O),
thionitrosamine groups (.dbd.N--N.dbd.S), nitramine groups
(.dbd.N--NO.sub.2), thionitramine groups (.dbd.N--NS.sub.2),
carbonylnitrene groups (--CO--N), thiocarbonylnitrene groups
(--CS--N), sulfenyl halides (--S--X), sulfoxides (--S.dbd.O),
sulfones (.dbd.S[.dbd.O].sub.2), sulfinyl groups (--N.dbd.S.dbd.O),
thiosulfinyl groups (--N.dbd.S=S), sulfenyl thiocyanato groups
(--S--S--CN), sulfenyl cyanato groups (--S--O--CN), sulfodiimine
groups (.dbd.S[.dbd.NH].sub.2), sulfur dihaloimido groups
(--N.dbd.SX.sub.2), sulfur oxide dihaloimido groups
(--N.dbd.S[.dbd.O]X.sub.2), aminosulfur oxide trihalide groups
(.dbd.N--S[.dbd.O]X.sub.3), sulfonyl azide groups
(--S[.dbd.O].sub.2N.sub- .3), sulfonyl thiocyanate groups
(--S[.dbd.O].sub.2SCN), sulfonyl cyanate groups
(--S[.dbd.O].sub.2OCN), sulfonyl cyanide groups (--S
[.dbd.O].sub.2CN), halosulfonate groups (--S[.dbd.O].sub.2OX),
phosphonyl thiocyanate groups (--P[.dbd.O]OHSCN), phosphonyl
cyanate groups (--P[.dbd.O]OHOCN), and phosphonyl cyanide groups
(--P[.dbd.O]OHCN). In this way, the characteristics of less typical
coordinating ligands may be adjusted so that the resultant MnIII-
or MnIV-valence stabilizer compound does exhibit some degree of
corrosion inhibition. Conversely, the physical characteristics of
typical coordination compounds can be adjusted so that they are no
longer suitable as a corrosion inhibitor.
[0090] Valence stabilizers can be either organic or inorganic
compounds. Manganese coordination chemistry, which has been the
subject of numerous scientific studies for almost 100 years,
identifies chemical binding preferences, structure stability, and
the physical properties of the resulting compounds. Producing
effective MnIII- and/or MnIV-valence stabilizer compounds requires
understanding the electrostatic and structural influence of
candidate species on the compound. The solubility of the valence
stabilized MnIII- and/or MnIV-compound scales roughly with the
inverse of its diameter. The MnIII and MnIV ions and their layer of
negatively charged hydroxyl ions are very small, which results in a
high degree of aqueous solubility. The field strength of the
complex also scales with the inverse of its physical diameter.
Large compounds with an optimal degree of solubility will not
necessarily be ideal with respect to the size of their
electrostatic double layer. The size of the ligand must therefore
be balanced against the desired electrical properties. The MnIII
ion generally favors complexation either in the square pyramidal
(coordination number 5) or octahedral (coordination number 6)
arrangements, although it will occasionally be found in a
pentagonal bipyramid arrangement. The MnIV ion almost exclusively
favors complexation in the octahedral (coordination number 6)
arrangement. Valence stabilizers (and stabilizer combinations)
should be selected with the goal of achieving these
coordinations.
[0091] Stabilizers can be designed that result in manganese
compounds with the necessary physical, electrical, and chemical
properties to perform as corrosion inhibitors with this
information. The nature of a particular valence stabilizer shell
surrounding the manganese ion, or combination of valence
stabilizers, can be further manipulated by the selection of
appropriate "shaping groups" and heteroatoms at the binding site.
Inorganic valence stabilizers are typically oxygen-containing
coordinations. Therefore, manipulation of different sized ionic
complexes around the MnIII or MnIV ions is best controlled through
adjustment of the heteroatoms (e.g., Mo, W, Te, etc.) within these
"polymerized" oxygen-containing ionic complexes (ligands).
[0092] For organic compounds, the physical geometry of the binding
sites is important to the stability of the MnIII- or
MnIV-stabilizer compound. The influence of site geometry becomes
evident when the solvation shell of a MnIII or MnIV ion is replaced
by the ligand donor atoms as when pigments are formed. The number
of available ligand binding sites should be at least equal to the
standard coordination number of the MnIII or MnIV ion. The balance
between solvation of the ligand and MnIII and/or MnIV and their
complexation where MnIII or MnIV is solvated by a specific ligand
is critical in maintaining stability. MnIII- or MnIV-ligand
attraction increases with the number of available binding sites on
the ligand. However, with an increasing number of binding sites,
site-site repulsions will also increase, resulting in lower
stability.
[0093] The number of binding sites available on the complexing
ligand is important to the resulting MnIII- or MnIV-stabilizer's
properties. Several ligands are required to effectively stabilize
MnIII or MnIV if the chosen ligand has only one binding site. For
example, six NH.sub.3 ligands are needed to octahedrally coordinate
MnIII in a hexaaminemanganese(III) compound because NH.sub.3 has
only one binding site. Bulky ligands with only one binding site,
like pyridine, can be sterically hindered from packing tightly
around the ion and will result in decreased compound stability.
Conversely, macrocyclic organic and polymeric inorganic ligands can
have many suitable binding sites. However, instability will result
if a MnIII or MnIV ion is not completely embraced by all of the
multiple macromolecular bonding sites on the ligand. For example,
if a macromolecule surrounding the MnIII or MnIV ion has an
insufficient number of binding sites available for charge balance,
then the MnIII- or MnIV-stabilizer compound will be much less
stable than a macromolecule that contains an adequate number of
sites.
[0094] The stability of the MnIII- or MnIV-organic compound is
strongly influenced by the charge, charge sign, and degree of
polarizability of specific binding sites. Factors influencing
compound stability include: 1) ion-pair interactions for charged
ligands and MnIII or MnIV; 2) ion-dipole and ion-induced dipole
interactions for neutral ligands; 3) hydrogen bonding; and 4) the
hard-soft acid-base (HSAB) rules convention of coordination
chemistry. HSAB rules help identify functional groups on ligands
that might be effective as binding sites. Optimum binding for
organic valence stabilizers to MnIII or MnIV will be with ligands
with hard bonding species such as those that contain oxygen or
nitrogen. Certain coordination complexes of the soft base sulfur
are also effective for binding with MnIII or MnIV. HSAB rules can
also help identify groups that might provide a degree of
polarization to the stabilizer because of their large dipole
moments. The nature-of bonding-between the MnIII or MnIV ion/oxide
cluster and the stabilizer ligand can be altered by using a
substituent group to modify the stabilizer. Specific interactions
between the ligand and MnIII or MnIV can be tailored by substituent
group selection coupled with altering the size or geometry of the
complexing ligand. Some substituent groups, such as carbonyls
(ketones, amides, ureas), nitro groups, cyano groups, and azido
groups have large dipole moments. The polarization of the MnIII- or
MnIV-stabilizer can therefore be optimized via evaluation of the
effect of ligand type and substituents.
[0095] Finally, the size of the valence stabilizer plays an
important role in solubility control of the resultant MnIII- or
MnIV-valence stabilizer compound. As the ligand increases in size,
it becomes more difficult to keep it in solution, therefore
lowering the solubility. However, this must be balanced against the
fact that as ligands are increased in size, it also becomes more
difficult to establish the necessary dipoles at the compound/water
interface. The size of the ligand must therefore be balanced
against the desired electrical properties. The addition (or
subtraction) of functional groups on organic valence stabilizers
can be used to modify the solubility of the formed Mn.sup.+3 or
Mn.sup.+4/valence stabilizer species. For example, the addition of
sulfonated groups (--SO.sub.3.sup.-) to organic valence stabilizers
will significantly increase the solubility in water. Other
substituent groups that will increase the solubility in water
include: carboxyl groups (--CO.sub.2--), hydroxyl groups (--OH),
ester groups (--CO.sub.3--), carbonyl groups (.dbd.C.dbd.O), amine
groups (--NH.sub.2), nitrosamine groups (.dbd.N--N.dbd.O),
carbonylnitrene groups (--CO--N), sulfoxide groups (.dbd.S.dbd.O),
sulfone groups (.dbd.S[.dbd.O].sub.2), sulfinyl groups
(--N.dbd.S.dbd.O), sulfodiimines (.dbd.S[.dbd.NH].sub.2), sulfonyl
halide groups (--S[.dbd.O].sub.2X), sulfonamide groups
(--S[.dbd.O].sub.2NH.sub.2), monohalosulfonamide groups
(--S[.dbd.O].sub.2NHX), dihalosulfonamide groups
(--S[.dbd.O].sub.2MX.sub- .2), halosulfonate groups
(--S[.dbd.O].sub.2OX), halosulfonate amide groups
(.dbd.N--S[.dbd.O].sub.2X), aminosulfonate groups
(.dbd.N--S[.dbd.O].sub.2OH), iminodisulfonate groups
(--N[SO.sub.3.sup.-].sub.2), phosphonate groups
(--PO.sub.3.sup.-2), phospbonamide groups
(--PO.sub.2NH.sub.2.sup.-), phosphondiamide groups
(--PO[NH.sub.2].sub.2), aminophosphonate groups
(--N--PO.sub.3.sup.-2), and iminodiphosphonate groups
(--N[PO.sub.3.sup.-2].sub.2). Conversely, the addition of nitro
groups (--NO.sub.2), perfluoroalkyl groups (--C.sub.xF.sub.2x+1),
perchloroalkyl groups (--C.sub.xCl.sub.2x+1), nitramine groups
(--N--NO.sub.2), thioketone groups (.dbd.C.dbd.S), sulfenyl halide
groups (--S--X), and sulfur dibaloimide groups (--N.dbd.SX.sub.2)
to organic valence stabilizers will decrease the solubility in
water. In this way, the solubility characteristics of valence
stabilizers can be "tailored" to meet specific binder/resin
needs.
[0096] Valence stabilizers-and combinations of stabilizers can be
manipulated by the selection of "shaping groups" and heteroatoms
positioned at the binding site. Saturated organic chains can form
flexible ligands that wrap around MnIII- or MnIV- and can enhance
their stability. Unsaturated organics typically have less freedom
to bend and contort and are less likely to be a ligand that can
wrap or fit around the MnIII or MnIV ions. Addition of substituents
onto an organic ligand may further restrict its freedom to flex.
For example, the attachment of a phenyl group onto an organic
valence stabilizer that contains two or more binding sites will
likely restrict the ability of that ligand to flex around the MnIII
or MnIV ions so as to coordinate it as a square pyramid or
octahedral complex.
[0097] The physical, chemical, and electrostatic requirements for
the design of effective pigments based on MnIII- or MnIV-stabilizer
compounds result in lists of stabilizers that may be divided into
wide band or narrow band stabilizer classes for MnIII or MnIV,
depending upon the application. Wide band valence stabilizers can
be used under a wide variety of service conditions (e.g., corroding
specie, temperature, etc.) to achieve a high degree of corrosion
resistance. Wide band physical properties (stability, solubility,
and polarization) can be achieved by both inorganic or organic
valence stabilizers. The desirable physical property of ion
exchange can also be achieved with both inorganic and organic
coordination compounds. "Narrow band" valence stabilizers result in
satisfactory pigments only under limited applications. Table 3
lists the wide and narrow band valence stabilizers for MnIII and
MnIV depending upon the specific application.
[0098] The compounds listed here are general guides for the initial
selection of a coordination compound and do not represent a
complete list. Tailoring substituent groups and the selection of
cations or anions for charge balance can influence whether a
particular MnIII- or MnIV-stabilizer compound will have wide band
or narrow band corrosion inhibiting characteristics. Both inorganic
or organic valence stabilizers may form compounds with the
necessary physical properties of stability, solubility, and
polarization to be effective corrosion inhibiting pigments.
4TABLE 3 Wide and Narrow Band Valence Stabilizers for Trivalent
and/or Tetravalent Manganese Replacements for Hexavalent Chromium
or Tetravalent Lead Pigments Hexavalent Chromium Wide Narrow or
Tetravalent Lead Band Valence Band Valence Pigment to be Replaced
Stabilizers Stabilizers Zinc Chromates Inorganic: Inorganic:
(including basic forms) Molybdates, tungstates, Bismuthates,
Strontium Chromates vanadates, niobates, germanates, Calcium
Plumbate tantalates, tellurates, arsenates periodates, iodates,
antimonates, stannates, sulfates, polyphosphates Organic: Organic:
See Table 4 See Table 5 Lead Chromates Inorganic: Inorganic:
(including basic forms) Oxygen, titanates, Carbonates Lead
Molybdate-Chromate zirconates, tantalates, Lead Silicochromate
aluminates, silicates, phosphates, borates Organic: Organic: none
none Red Lead Inorganic: Inorganic: Oxygen, titanates, None
zirconates, tantalates, aluminates, silicates Organic: Organic:
none none
[0099] 3a) Wide Band Inorganic Valence Stabilizers
[0100] Wide band inorganic valence stabilizers are formed around
the MnIII or MnIV ion by "polymerizing" in synthesis solution.
Inorganic wide band valence stabilizers for MnIII or MnIV for
"sparingly soluble" pigments include molybdates (Mo.sup.+6,
Mo.sup.+5, or Mo.sup.+4, for example
[Mn.sup.+4Mo.sub.9O.sub.32].sup.6- and
[Mn.sup.+4Mo.sub.12O.sub.40].sup.4- -), tungstates (W.sup.+6,
W.sup.+5, or W.sup.+4, for example
[Mn.sup.+4W.sub.12O.sub.40].sup.4- and
[Mn.sup.+3.sub.2W.sub.22O.sub.74].- sup.10-), vanadates (V.sup.+5
and V.sup.+4, for example [Mn.sup.+4V.sub.13O.sub.38].sup.7- and
[Mn.sup.+4V.sub.11O.sub.32].sup.5-- ), niobates (Nb.sup.+5 and
Nb.sup.+4, for example [Mn.sup.+4Nb.sub.12O.sub- .38].sup.12-),
tantalates (Ta.sup.+5 and Ta.sup.+4, for example
[Mn.sup.+4Ta.sub.12O.sub.38].sup.12-), tellurates (Te.sup.+6 and
Te.sup.+4, for example [Mn.sup.+4Te.sub.3O.sub.18].sup.14-),
periodates (1.sup.+7, for example
[Mn.sup.+4I.sub.3O.sub.18].sup.11-), iodates (1.sup.+5, for example
[Mn.sup.+4I.sub.6O.sub.18].sup.2-), antimonates (Sb.sup.+5 and
Sb.sup.+3), stannates (Sn.sup.+4), sulfates (S.sup.+6, such as
manganese spinels [Mn.sup.+3(SO.sub.4).sub.2].sup.1-), and
polyphosphates (P.sup.+5, for example
[Mn.sup.+3P.sub.3O.sub.10].sup.2- and
[Mn.sup.+3P.sub.2O.sub.7].sup.1-). Many of these inorganics form
octahedral and square pyramidal heteropolymetallate structures on
precipitation from solution. For example, tellurate ions begin to
polymerize near pH 5 in water and will complex with MnIII or MnIV
ions in basic solution pH's. Therefore, as the pH is raised in the
pigment synthesis bath, the tellurate ion polymerizes to
polymorphs, which then complex the MnII or MnIV ion.
[0101] The general structural aspects of heteropolymetallates are
well understood, and the stability of heteropolymetallates as a
function of composition and structure is also well-characterized.
The relatively unstable MnIII or MnIV ions are protected and
stabilized within the surrounding octahedral and square pyramidal
groups, although specific configurations of the heteropolymetallate
anions differ from stabilizer to stabilizer (i.e., from molybdate
to periodate or iodate). The dimensions of the octahedra and square
pyramids are controlled by the size of the heteroatom (e.g., Mo, W,
or Te) around which they are assembled.
[0102] A MnIII or MnIV ion trapped by the precipitation of these
heteropolymetallates and its resulting "ion within a cage"
structure can exhibit an even greater apparent volume due to the
development of a large electrostatic double layer. This will
influence both the valence stabilization of the MnIII or MnIV, as
well as the solubility of the assembled compound. These compounds
are reported to be excellent ion exchange agents for alkali ions.
This caging structure serves to lower the solubility of the MnIII
or MnIV because the chemical elements typically associated with
these valence stabilizers (e.g., I, Te, Mo, or W) are all
inherently less soluble in water than Mn. These materials can also
establish oriented dipoles with the interior MnII or MnIV ion and
form an electrostatic double layer during aqueous corrosion.
Finally, the elements associated with these valence stabilizers
themselves can contain high valence ions (i.e., V.sup.+5,
Te.sup.+6, or Mo.sup.+6), which will also serve somewhat in
corrosion protection, although not to the degree of MnIII or MnIV
(or CrVI), due to their lower redox potential.
[0103] Water-soluble precursors for these materials are generally
used so that the synthesis can be carried out from aqueous
solution. Many elements associated with these stabilizers (e.g.,
Mo, W, or Te) do not typically form water-soluble compounds so the
identification of suitable precursors can be difficult.
[0104] Complex, partially-polymerized salts such as para- or
meta-polymorphs for each compound may also be used as precursors.
These polymorphs typically exhibit slightly lower solubilities in
water than the simple salts. Peroxo-salts of these compounds,
especially permolybdates, pertungstates, and pervanadates may also
be used as precursors. Formation of the chosen heteropolymetallates
from precursors such-as the fluorides, chlorides, bromides,
nitrates, and perchlorates (e.g., SnCl.sub.4 to form
heterostannates and SbF.sub.5 to form heteroantimonates) can be
difficult, but may be acceptable in certain circumstances. A
valence stabilizer can be a cross between two or more of the
wide-band inorganic valence stabilizers listed above. For example,
a valence stabilizer composed of a periodate and a molybdate may be
desirable in some situations. During the synthesis process, both of
these materials will polymerize to form a mixed periodate/molybdate
valence stabilizer out of the pigment solution.
[0105] The most notable valence stabilizer for low and insoluble
MnIII and MnIV pigments is oxygen (O), as evidenced by the natural
stability of such compounds as MnO.sub.2, Mn.sub.3O.sub.4,
Mn.sub.2O.sub.3 and MnOOH, all of which contain MnIII and/or MnIV
ions. In instances where oxygen is used as a valence stabilizer for
MnIII or MnIV, differences in addendum cations (i.e., Ca.sup.+2 in
CaMn.sub.2O.sub.4 or Zn.sup.+2 in ZnMn.sub.2O.sub.4) are observed
to alter the solubility of the formed compound, and its performance
as a corrosion inhibitor in a given binder system. This is
discussed under Section 4 describing Additional Solubility Control
Agents.
[0106] Additional wide band valence stabilizers for MnIII or MnIV
for "low solubility" or "insoluble" pigments include silicates
(Si.sup.+4, for example [Mn.sup.+3Si.sub.2O.sub.6].sup.1-), borates
(B.sup.+3, for example Mn.sup.+3.sub.2B.sub.4O.sub.9), phosphates
(P.sup.+5, for example Mn.sup.+3PO.sub.4), titanates (Ti.sup.+4),
zirconates (Zr.sup.+4), and aluminates (Al.sup.+3). These compounds
can also form octahedral or square pyramids, but have a higher
tendency to form chain-like structures during calcining or firing.
Combinations of these materials, such as phosphosilicates,
aluminosilicates, or borosilicates may also function as wide band
valence stabilizers for low and insoluble MnIII and MnIV
compounds.
[0107] 3b) Wide Band Organic Valence Stabilizers
[0108] A variety of organic compounds meet the criteria to be
typical wide band valence stabilizers for MnIII or MnIV. These
coordination ligands produce MnIII or MnIV valence stabilized
compounds that fulfill the general requirements of a MnIII or MnIV
pigment material. Organic compounds can be very effective manganese
stabilizers and provide the greatest degree of freedom in designing
new manganese-stabilizer compounds with new functionalities. More
possible organic valence stabilizer species exist than inorganic
valence stabilizers because of the immense number of organic
compounds and functionalities from which to choose. Water-soluble
precursors for the organic valence stabilizers are generally used
so that pigment synthesis can be carried out in aqueous solution.
However, alcohol or hydrocarbon soluble species can also be
used.
[0109] The number of wide band (and narrow band) organic compounds
that are acceptable as valence stabilizers for trivalent or
tetravalent manganese is limited. Common organic compounds such as
alcohols, aldehydes, ketones, esters, ethers, alkyl or aromatic
halides, most carboxylic acids, anhydrides, phenols, sulfonic
acids, phosphonic acids, carbohydrates, waxes, fats, sugars, and
oils are not as effective as the structural types described in
these Tables to stabilize the trivalent or tetravalent manganese
ion. At best, some of the organic types described in these Tables
may presently be used for other industrial applications, but their
incorporation into corrosion-inhibiting blends to stabilize
trivalent or tetravalent manganese has heretofore been
unrecognized.
[0110] The choice of substituent functional groups on these general
classes of valence stabilizers will affect the physicochemical
properties of the MnIII- or MnIV-containing compound and the
corrosion resistance achieved using that compound. For example, the
addition of --NH.sub.2 or .dbd.O substituents increases the net
polarization of the overall net MnIII or MnIV/valence stabilizer
compound, but will also increase its water solubility. Careful
molecular design of MnIII and MnIV compounds is necessary in order
to achieve desired performance characteristics.
[0111] In general, the bonding atoms in typical organic valence
stabilizers are nitrogen, oxygen, or sulfur. Bonding atoms such as
phosphorus, carbon, silicon, tin, arsenic, and antimony are much
less desirable due to problems with valence stability, toxicity, or
solubility. Other stable coordinations (like pentagonal
bipyramidal) are known, even though these particular agents prefer
octahedral or square pyramidal coordination with Mn.sup.+3 or
Mn.sup.+4. These valence stabilizers all serve to stabilize the
Mn.sup.+3 or Mn.sup.+4 ions within a sparingly soluble complex that
can exhibit a polar character in aqueous solution.
5TABLE 4 Wide Band Organic Valence Stabilizers for the Mn.sup.+3
and Mn.sup.+4 Ions General Structural Name (Type of Organic)
Structural Representation N Valence Stabilizer #1: NH.sub.3,
NH.sub.2R, NHR.sub.2, and NR.sub.3 where R Monoamines represents H
or any organic functional group (N Monodentates) wherein the number
of carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/ solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #2: R'--N--R--N--R", where R, R', and R" Diamines
represent H or any organic functional group (N--N Bidentates)
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/ solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #3: R--N--R'--N--R"--N--R''', where R,
R', Triamines (either N--N R", and R''' represent H or any organic
Bidentates or N--N functional group wherein the number of carbon
Tridentates) atoms ranges from 0 to 40, optionally having halogen
or polarizing or water-insolubilizing/ solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #4: R--N--R'--N--R"--N--R"'--N--R"", Tetramines
(N--N where R, R', R", R"', and R"" represent H or Bidentates, N--N
any organic functional group wherein the Tridentates, or N--N
number of carbon atoms ranges from 0 to 40, Tetradentates)
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #5:
R--N--R'--N--R"--N--R"'--N- --R""-- Pentamines (N--N N--R""', where
R, R', R", R"', R"", and Bidentates, N--N R""' represent H or any
organic functional Tridentates, or N--N group wherein the number of
carbon atoms Tetradentates) ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #6: R--N--R'--N--R"--N--R"'--N--R""-- Hexamines
(N--N N--R""'--N--R""", where R, R', R", R"', Bidentates, N--N R"",
R""', and R""" represent H or any Tridentates, N--N organic
functional group wherein the number Tetradentates, or N--N of
carbon atoms ranges from 0 to 40, Hexadentates) optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #7: Five membered heterocyclic ring containing
Five-Membered Heterocyclic one, two, three, or four nitrogen atoms,
all of Rings containing One, which may or may not function as
binding Two, Three, or Four sites. Can include other ring systems
bound Nitrogen Atoms wherein at to this heterocyclic ring, but they
do not least one Nitrogen Atom is coordinate with the stabilized,
high valence a Binding Site (N metal ion. Ring can also contain O,
S, or P Monodentates or N--N atoms. This 5-membered ring and/or
Bidentates) attached, uncoordinating rings may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. N Valence Stabilizer #8: Six membered heterocyclic ring
containing Six-Membered Heterocyclic one, two, three, or four
nitrogen atoms, all Rings containing One, of which may or may not
function as binding Two, Three, or Four sites. Can include other
ring systems bound Nitrogen Atoms wherein at to this heterocyclic
ring, but they do not least one Nitrogen Atom is coordinate with
the stabilized, high valence a Binding Site (N metal ion. Ring can
also contain O, S, or Monodentates or N--N P atoms. This 6-membered
ring and/or Bidentates) attached, uncoordinating rings may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N Valence Stabilizer
#9: Five membered heterocyclic ring(s) Five-Membered Heterocyclic
containing one, two, three, or four nitrogen Rings containing One,
atoms. In addition, ligand contains additional Two, Three, or Four
nitrogen-containing substituents (usually Nitrogen Atoms and having
amines) that constitute N binding sites. Can at least one
additional include other ring systems bound to the Nitrogen Atom
Binding heterocyclic ring or to the N-containing Site not in a Ring
(N substituent, but they do not coordinate with Monodentates, N--N
the stabilized, high valence metal ion. Bidentates, N Ring(s) can
also contain O, S, or P atoms. Tridentates, N--N This 5-membered
ring(s) and/or attached, Tetradentates, or uncoordinating rings
and/or N containing N--N Hexadentates) substituent(s) may or may
not have halogen or polarizing or water-insolubilizing/
solubilizing groups attached. N Valence Stabilizer #10: Six
membered heterocyclic ring(s) Six-Membered Heterocyclic containing
one, two, three, or four nitrogen Rings containing One, atoms. In
addition, ligand contains additional Two, Three, or Four
nitrogen-containing substituents (usually Nitrogen Atoms at least
one amines) that constitute N binding sites. Can additional
Nitrogen Atom include other ring systems bound to the Binding Site
not in a Ring heterocyclic ring or to the N-containing (N
Monodentates, N--N substituent, but they do not coordinate with
Tridentates, N--N the stabilized, high valence metal ion.
Tetradentates, or N--N Ring(s) can also contain O, S, or P atoms.
Bidentates, N--N This 6-membered ring(s) and/or attached,
Hexadentates) uncoordinating rings and/or N-containing
substituent(s) may or may not have halogen or polarizing or
water-insolubilizing/ solubilizing groups attached. N Valence
Stabilizer #11:. Five membered heterocyclic ring(s) Five-Membered
Heterocyclic containing one, two, three, or four nitrogen Rings
containing One, atoms. In addition, ligand contains additional Two,
Three, or Four nitrogen-containing rings that constitute N Nitrogen
Atoms at least binding sites. Can include other ring systems one
additional Nitrogen bound to the N-containing heterocyclic rings,
Atom Binding Site in a but they do not coordinate with the Separate
Ring (N stabilized, high valence metal ion. Ring(s) Monodentates,
N--N can also contain O, S, or P atoms. This Bidentates, N--N
5-membered ring(s) and/or additional N- Tridentates, N--N
containing ring(s) and/or attached, Tetradentates) uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N Valence Stabilizer
#12: Six membered heterocyclic ring(s) Six-Membered Heterocyclic
containing one, two, three, or four nitrogen Rings containing One,
atoms. In addition, ligand contains additional Two, Three, or Four
nitrogen-containing rings that constitute N Nitrogen Atoms at least
one binding sites. Can include other ring systems additional
Nitrogen Atom bound to the N-containing heterocyclic Binding Site
in a Separate rings, but they do not coordinate with the Ring (N
Monodentates, stabilized, high valence metal ion. Ring(s) N--N
Bidentates, N--N can also contain O, S, or P atoms. This
Tridentates, N--N 6-membered ring(s) and/or additional N-
Tetradentates) containing ring(s) and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N Valence Stabilizer
#13: Macrocyclic ligands containing two, three, Two-, Three-,
Four-, Six-, four, six, eight, or ten nitrogen binding sites
Eight-, and Ten- Membered to valence stabilize the central metal
ion. Macrocyclics, Can include other hydrocarbon or ring
Macrobicyclics, and systems bound to this macrocyclic ligand,
Macropolycyclies but they do not coordinate with the (including
Catapinands, stabilized, high valence metal ion. This Cryptands,
Cyclidenes, and ligand and/or attached, uncoordinating
hydrocarbons/rings may or may Sepulchrates) wherein all not have
halogen or polarizing or water- Binding Sites are composed
insolubilizing/solubilizing groups attached. of Nitrogen (usually
amine or imine groups) and are not contained in Component
Heterocyclic Rings (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) N Valence Stabilizer #14:
Macrocyclic ligands containing a total of Four-, Six-, Eight-, or
four, six, eight, or ten five-membered Ten-Membered Macro-
heterocyclic rings containing nitrogen cyclics, Macrobicyclics,
binding sites. Can include other and Macropolycyclics
hydrocarbon/ring systems bound to this (including Catapinands,
macrocyclic ligand, but they do not Cryptands, Cyclidenes, and
coordinate with the stabilized, high valence Sepulchrates) wherein
all metal ion. This ligand and/or attached, Binding Sites are
composed uncoordinating hydrocarbon/rings may or of Nitrogen and
are may not have halogen or polarizing or contained in Component
water-insolubilizing groups attached. 5-Membered Heterocyclic Rings
(N--N Bidentates, N--N Tridentates, N--N Tetradentates, or N--N
Hexadentates) N Valence Stabilizer #15: Macrocyclic ligands
containing at least one Four-, Six-, Eight-, or Ten- 5-membered
heterocyclic ring. These Membered Macrocyclics, heterocyclic rings
provide nitrogen binding Macrobicyclics, and sites to valence
stabilize the central metal Macropolycyclics ion. Other amine or
imine binding sites can (including Catapinands, also be included in
the macrocyclic ligand, Cryptands, Cyclidenes, so long as the total
number of binding sites and Sepulchrates) is four, six, eight, or
ten. Can include other wherein all Binding Sites hydrocarbon/ring
systems bound to this are composed of Nitrogen macrocyclic ligand,
but they do not and are contained in a coordinate with the
stabilized, high valence Combination of 5- metal ion. This ligand
and/or attached, Membered Heterocyclic uncoordinating
hydrocarbon/rings may or may Rings and Amine or Imine not have
halogen or polarizing or water- Groups (N--N Bidentates,
insolubilizing groups attached. N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) N Valence Stabilizer #16:
Macrocyclic ligands containing a total of Four-, Six-, Eight-, or
Ten- four, six, eight, or ten six-membered Membered Macrocyclics,
heterocyclic rings containing nitrogen Macrobicyclics, and binding
sites. Can include other Macropolycyclics hydrocarbon/ring systems
bound to this (including Catapinands, macrocyclic ligand, but they
do not Cryptands, Cyclidenes, and coordinate with the stabilized,
high valence Sepulchrates) wherein all metal ion. This ligand
and/or attached, Binding Sites are composed uncoordinating
hydrocarbon/rings may or of Nitrogen and are may not have halogen
or polarizing or water- contained in Component insolubilizing
groups attached. 6-Membered Heterocyclic Rings (N--N Bidentates,
N--N Tridentates, N--N Tetradentates, or N--N Hexadentates) N
Valence Stabilizer #17: Macrocyclic ligands containing at least one
Four-, Six-, Eight-, or Ten- 6-membered heterocyclic ring. These
Membered Macrocyclics, heterocyclic rings provide nitrogen binding
Macrobicyclics, and sites to valence stabilize the central metal
Macropolycyclics ion. Other amine or imine binding sites can
(including Catapinands, also be included in the macrocyclic ligand,
Cryptands, Cyclidenes, so long as the total number of binding and
Sepulchrates) sites is four, six, eight, or ten. Can include
wherein all Binding Sites other hydrocarbon/ring systems bound to
are composed of Nitrogen this macrocyclic ligand, but they do not
and are contained in a coordinate with the stabilized, high valence
Combination of 6- metal ion. This ligand and/or attached, Membered
Heterocyclic uncoordinating hydrocarbon/rings may or Rings and
Amine or Imine may not have halogen or polarizing or water- Groups
(N--N Bidentates, insolubilizing groups attached. N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) N Valence Stabilizer #18:
R'--NH--C(--R).dbd.N--R", where R, R', Amidines and Diamidines and
R"represent H or any organic functional (N--N Bidentates and group
wherein the number of carbon atoms N--N Tetradentates) ranges from
0 to 40, optionally having halogen or polarizing or
water-insolubilizing/ solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #19:
RR'--N--C(.dbd.NH)--NR"--C(.dbd.N- H)-- Biguanides NR"'R"" for
biguanides, RR'--N-- (Imidodicarbonimidic
C(.dbd.NH)--NR"--NH--C(.dbd.NH)--NR"'R"" Diamides or Dihydrazides),
for biguanidines, where R, R', R", R"', and Biguanidines, R""
represent H, NH.sub.2, or any organic Imidotricarbonimidic
functional group wherein the number of Diamides or Dihydrazides,
carbon atoms ranges from 0 to 40, halogen Imidotetracarbonimidic or
polarizing or water-insolubilizing/ Diamides or Dihydrazides,
solubilizing groups attached. Ligand can also Dibiguanides, contain
nonbinding N, O, S, or P atoms. Bis(biguanidines), Polybiguanides,
and Poly(biguanidines) (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) N Valence Stabilizer #20:
RR'--N--C(.dbd.NH)--CR"R'"--C(.dbd.NH)-- Diamidinomethanes,
NR""R""', where R, R', R", R"', R"", and Bis(amidinomethanes), and
R""' represent H, NH.sub.2, or any organic Poly(amidinomethanes)
functional group wherein the number of (N--N Bidentates, N--N
carbon atoms ranges from 0 to 40, optionally Tridentates, N--N
having halogen or polarizing or water- Tetradentates, and
insolubilizing/solubilizing groups attached. N--N Hexadentates)
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #21: RR'--N--C(.dbd.NH)--NR"--C(.dbd.NH)--R"'
Imidoylguanidines, for imidoylguanidines, and RR'--N--
Amidinoguanidines, C(.dbd.NH)--NR"--NH--C(NH)--R"' for
Bis(imidoylguanidines), amidinoguanidines, where R, R', R", and
Bis(amidinoguanidines), R"' represent H, NH.sub.2, or any organic
Poly(imidoylguanidines), functional group wherein the number of and
Poly(amidino- carbon atoms ranges from 0 to 40, optionally
guanidines) (N--N having halogen or polarizing or water-
Bidentates, N--N insolubilizing/solubilizing groups attached.
Tridentates, N--N Ligand can also contain nonbinding N, O, S,
Tetradentates) or P atoms. N Valence Stabilizer #22:
RR'--N--C(NH)--O--C(.dbd.NH)-NR"R"', Diformamidine oxides where R,
R', R", and R"' represent H, NH.sub.2, (Dicarbonimidic Diamides or
any organic functional group wherein the or Dihydrazides), number
of carbon atoms ranges from 0 to 40, Tricarbonimidic Diamides
optionally having halogen or polarizing or or Dihydrazides,
water-insolubilizing/solubilizing groups Tetracarbonimidic
attached. Ligand can also contain nonbinding Diamides or
Dihydrazides, N, O, S, or P atoms. Bis(diformamidine oxides), and
Poly(diformamidine oxides) (N--N Bidentates, N--N Tridentates, N--N
Tetradentates) N Valence Stabilizer #23:
RR'--N--C(.dbd.NH)--S--C(.dbd.NH)-- Diformamidine Sulfides NR"R"',
where R, R', R", and R"' represent (Thiodicarbonimidic H, NH.sub.2,
or any organic functional group Diamides or Dihydrazides), wherein
the number of carbon atoms ranges Thiotricarbonimidic from 0 to 40,
optionally having halogen or Diamides or Dihydrazides, polarizing
or water-insolubilizing/ Thiotetracarbonimidic solubilizing groups
attached. Ligand can also Diamides or Dihydrazides, contain
nonbinding N, O, S, or P atoms. Bis(diformamidine sulfides), and
Poly(diformamidine sulfides) (N--N Bidentates, N--N Tridentates,
N--N Tetradentates) N Valence Stabilizer #24:
R--O--C(.dbd.NH)--NR'--C(- .dbd.NH)--O--R' Imidodicarbonimidie
Acids, for imidodicarbomimidic acids, and R--O--
Diimidodicarbonimidic C(.dbd.NH)--NR'--NH--C(.db-
d.NH)--O--R" Acids, Imidotricarbon- for diimidodicarbonimidic
acids, where R, imidic Acids, Imidotetra- R', and R" represent H,
NH.sub.2, or any organic carbonimidic Acids, and functional group
wherein the number of derivatives thereof (N--N carbon atoms ranges
from 0 to 40, optionally Bidentates, N--N having halogen or
polarizing or water- Tridentates, N--N insolubilizing/solubilizing
groups attached. Tetradentates, and Ligand can also contain
nonbinding N, O, S, N--N Hexadentates) or P atoms. N Valence
Stabilizer #25: R--S--C(.dbd.NH)--NR'--C(.dbd.NH)--S--R"
Thioimidodicarbonimidic for thioimidodicarbonimidic acids, and R--
Acids, Thiodiimidodi- S--C(.dbd.NH)--NR'--NH--C(.dbd.NH)--S
carbonimidic Acids, --R" for thiodiimidodicarbonimidic acids,
Thioimidotricarbonimidic where R, R', and R" represent H, NH.sub.2,
or Acids, Thioimidotetra- any organic functional group wherein the
carbonimidic Acids, and number of carbon atoms ranges from 0 to 40,
derivatives thereof optionally having halogen or polarizing or
(N--N Bidentates, N--N water-insolubilizing/solubilizing groups
Tridentates, N--N attached. Ligand can also contain nonbinding
Tetradentates, and N, O, S, or P atoms. N--N Hexadentates) N
Valence Stabilizer #26: R--C(.dbd.NH)--NR'--C(.dbd.NH)--R" for
Diimidoylimines, diimidoylimines, and R--C(.dbd.NH)--NR'--
Diimidoylhydrazides, NH--C(.dbd.NH)--R" for diimidoyl-
Bis(diimidoylimines), hydrazides, where R, R', and R" represent
Bis(diimidoylhydrazides), H, NH.sub.2, or any organic functional
group Poly(diimidoylimines), and wherein the number of carbon atoms
ranges Poly(diimidoylhydrazides) from 0 to 40, optionally having
halogen or (N--N Tridentates and polarizing or
water-insolubilizing/ N--N Hexadentates) solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #27: RR'--N--S(.dbd.NH)(.dbd.O)--OR" or RR'--
Imidosulfamides, N--S(.dbd.NH)(.dbd.O)--N--R"R"' for
Diimidosulfamides, imidosulfamides, and RR'--N--
Bis(imidosulfamides), S(.dbd.NH)(.dbd.NH)--OR" or RR'--N--
Bis(diimidosulfamides), S(.dbd.NH)(.dbd.NH)--N--R"R"' for diimido-
Poly(imidosulfamides), and sulfamides, where R, R', R", and R"'
Poly(diimidosulfamides) represent H, NH.sub.2, or any organic
functional (N--N Bidentates, N--N group wherein the number of
carbon atoms Tridentates, N--N ranges from 0 to 40, optionally
having Tetradentates, and halogen or polarizing or
water-insolubilizing/ N--N Hexadentates) solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #28: (NH.dbd.)P(--NRR')(--NR"R"')(--NR""R""'),
Phosphoramidimidic where R, R', R", R"', R"", and R""' represent
Triamides, Bis(phosphor- H, NH.sub.2, or any organic functional
group amidimidic triamides), and wherein the number of carbon atoms
ranges Poly(phosphoramidimidic from 0 to 40, optionally having
halogen or triamides) and derivatives polarizing or
water-insolubilizing/ thereof (N--N Bidentates, solubilizing groups
attached. Ligand can also N--N Tridentates, N--N contain nonbinding
N, O, S, or P atoms. Tetradentates, and N--N Hexadentates) N
Valence Stabilizer #29: (NH.dbd.)P(--NRR')(OH).sub.2 for phosphor-
Phosphoramidimidic Acid, amidimidic acid, and (NH.dbd.)P(--NRR')
Phosphorodiamidimidic (--NR"R"')(OH) for phosphorodiamidimidic
Acid, Bis(Phosphor- acid, where R, R', R", and R"' represent H,
amidimidic Acid), NH.sub.2, or any organic functional group
Bis(Phosphorodiamidimidic wherein the number of carbon atoms ranges
Acid), Poly(Phosphor- from 0 to 40, optionally having halogen or
amidimidic Acid), and polarizing or water-insolubilizing/
Poly(Phosphorodi- solubilizing groups attached. Ligand can also
amidimidic Acid), contain nonbinding N, O, S, or P atoms.
derivatives thereof (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) N Valence Stabilizer #30:
(NH.dbd.)P(--NRR')(SH).sub.2 for phos- Phosphoramidimidodithioic
phoramidimidodithioic acid, and (NH.dbd.)P(-- Acid,
Phosphorodiamidi- NRR')(--NR"R"')(SH) for midothioic Acid,
Bis(Phos- phosphorodiamidimidothioic acid, where R,
phoramidimidodithioic R', R", and R"' represent H, NH.sub.2, or any
Acid), Bis(Phosphorodi- organic functional group wherein the number
amidimidothioic Acid), of carbon atoms ranges from 0 to 40,
Poly(Phosphoramidimido- optionally having halogen or polarizing or
dithioic Acid), Poly(Phos- water-insolubilizing/solubilizing groups
phorodiamidimidothioic attached. Ligand can also contain nonbinding
Acid), and derivatives N, O, S, or P atoms. thereof (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) N Valence Stabilizer #31: R--N.dbd.N--R' for azo
compounds, Azo compounds including R--N.dbd.--NH--R' for triazenes,
where triazenes with amino, R, and R' represent H or any organic
imino, oximo, diazeno, or functional group wherein the number of
hydrazido substitution at carbon atoms ranges from 0 to 40,
optionally the ortho- (for aryl) or having halogen or polarizing or
water- alpha- or beta- (for alkyl) insolubilizing/solubilizing
groups attached. positions, Bis[o-(H.sub.2N--) (Must include
ortho-amino, imino, oximo, or alpha- or beta- diazeno, or hydrazido
substituted aryl azo (H.sub.2N--)azo compounds], compounds, and
alpha- or beta-amino, or Poly[o-(H.sub.2N--) or imino, oximo,
diazeno, or hydrazido alkyl alpha- or beta-(H2N--)azo azo
compounds.) Ligand can also contain compounds) (N--N nonbinding N,
O, S, or P atoms. Bidentates, N--N Tridentates, N--N Tetradentates,
or N--N Hexadentates) N Valence Stabilizer #32:
R--N.dbd.N--C(.dbd.NH)--NR- 'R" for diazene- Diazeneformimidamides
formimidamides, and R--N.dbd.N--CR'R"-- (Diazeneamidines),
C(.dbd.NH)--NR"'R"" for diazeneacetimid- Diazeneacetimidamides
amides, where R, R', R", R"', and R"" (Diazene-alpha-amidino-
represent H, NH.sub.2, or any organic functional alkanes(alkenes)),
Bis(di- group wherein the number of carbon atoms
azeneformimidamides), ranges from 0 to 40, optionally having
Bis(diazeneacetimid- halogen or polarizing or water-insolubilizing/
amides), Poly(diazene- solubilizing groups attached. Ligand can
also formimidamides), and contain nonbinding N, O, S, or P atoms.
Poly(diazeneacetimid- amides) (N--N Bidentates, N--N Tetradentates,
and N--N Hexadentates) N Valence Stabilizer #33:
R--N.dbd.N--C(.dbd.NH)--OR' for diazene- Diazeneformimidic Acid,
formimidic acid, and R--N.dbd.N--CR'R"-- Diazeneacetimidic Acid,
C(.dbd.NH)--OR"' for diazeneacetimidic acid, Bis(diazeneformimidic
where R, R', R", and R"' represent H, NH.sub.2, acid), Bis(diazene-
or any organic functional group wherein the acetimidic acid),
number of carbon atoms ranges from 0 to 40, Poly(diazeneformimidic
optionally having halogen or polarizing or acid), Poly(diazene-
water-insolubilizing/solubilizing groups acetimidic acid), and
attached. Ligand can also contain nonbinding Bidentates, N--N N, O,
5, or P atoms. Tetradentates, and N--N Hexadentates) N Valence
Stabilizer #34: R--N.dbd.N--C(.dbd.NH)--SR' for diazene-
Diazeneformimidothioic formimidothioic acid, and R--NN-- Acid,
Diazeneacetimido- CR'R"--C(.dbd.NH)--SR"' for diazene- thioic Acid,
Bis(diazene- acetimidothioic acid, where R, R', R", and
formimidothioic acid), R"' represent H, NH.sub.2, or any organic
Bis(diazeneacetimidothio- ic functional group wherein the number of
acid), Poly(diazene- carbon atoms ranges from 0 to 40, optionally
formimidothioic acid), having halogen or polarizing or water-
Poly(diazeneacetimido- insolubilizing/solubilizing groups attached.
thioic acid), and Ligand can also contain nonbinding N, O, S,
derivatives thereof or P atoms. (N--N Bidentates, N--N
Tetradentates, and N--N Hexadentates) N Valence Stabilizer #35:
R--N.dbd.N--C(NH)--R' or R--N.dbd.N-- Imidoyldiazenes,
CR'R"--C(.dbd.NH)--R"', where R, R', R", Bis(imidoyldiazenes), and
and R"'represent H, NH.sub.2, or any organic Poly(imidoyldiazenes),
functional group wherein the number of (N--N Bidentates, carbon
atoms ranges from 0 to 40, optionally N--N Tetradentates having
halogen or polarizing or water- and N--N Hexadentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #36:
RR'--N--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)-- Diazenediformimidamides
NR"R"' for diazenediformimidamides, and (1,2-Diazenediamidines),
RR'--N--C(.dbd.NH)--CR"R"'--N.dbd.N-- Diazenediacetimidamides
CR""R""'--C(.dbd.NH)--NR"""R"""' (1,2-Diazene-di-alpha- for
diazenediacetimidamides, where R, R', amidinoalkanes(alkenes)), R",
R'", R"", R""', R""", and R"""' represent Bis(diazenediformimid- H,
NH.sub.2, or any organic functional group amides), Bis(diazenedi-
wherein the number of carbon atoms ranges acetimidamides), Poly(di-
from 0 to 40, optionally having halogen or azenediformimidamides),
polarizing or water-insolubilizing/ and Poly(diazenedi-
solubilizing groups attached. Ligand can also acetimidamides) (N--N
contain nonbinding N, O, S, or P atoms. Tridentates and N--N
Hexadentates) N Valence Stabilizer #37:
RO--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)--OR' Diazenediformimidic Acid,
for diazenediformimidic acid, and RO-- Diazenediacetimidic Acid,
C(.dbd.NH)--CR'R"--N.dbd.N--CR"'R""-- Bis(diazenediformimidic
C(.dbd.NH)--OR""' for diazenediacetimidic acid), Bis(diazenedi-
acid, where R, R', R", R"', R"", and R""' acetimidic acid),
represent H, NH.sub.2, or any organic functional
Poly(diazenediformimidic group wherein the number of carbon atoms
acid), and Poly(diazenedi- ranges from 0 to 40, optionally having
acetimidic acid), and halogen or polarizing or
water-insolubilizing/ derivatives thereof solubilizing groups
attached. Ligand can also (N--N Tridentates contain nonbinding N,
O, S, or P atoms. and N--N Hexadentates) N Valence Stabilizer #38:
RS--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)--SR' for
Diazenediformimidothioic diazenediformimidothioic acid, and RS--
Acid, Diazenediacetimido- C(.dbd.NH)--CR'R"--N.dbd.N--CR"'R""--
thioic Acid, Bis(diazene- C(.dbd.NH)--SR""' for diazenediacetimi-
diformimidothioic acid), dothioic acid, where R, R', R", R"', R"",
and Bis(diazenediacetimido- R""' represent H, NH.sub.2, or any
organic thioic acid), Poly(diazene- functional group wherein the
number of diformimidothioic acid), carbon atoms ranges from 0 to
40, optionally and Poly(diazenedi- having halogen or polarizing or
water- acetimidothioic acid), and insolubilizing/solubilizing
groups attached. derivatives thereof Ligand can also contain
nonbinding N, O, S, (N--N Tridentates and or P atoms. N--N
Hexadentates) N Valence Stabilizer #39:
R--C(.dbd.NH)--N.dbd.N--C(NH)--R"or Diimidoyldiazenes,
R--C(.dbd.NH)--CR'R"--N.dbd.N--CR"'R""-- Bis(diimidoyldiazenes),
C(.dbd.NH)--R""', where R, R', R", R"', R"", and Poly(diimidoyl-
and R""' represent H, NH.sub.2, or any organic diazenes), (N--N
functional group wherein the number of Tridentates and N--N carbon
atoms ranges from 0 to 40, optionally Hexadentates) having halogen
or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #40: R--N.dbd.N--CR'.dbd.N--NR"R"', where R, R',
Ortho-amino (or R", and R"' represent H, or any organic -hydrazido)
Substituted functional group wherein the number of Formazans,
Bis(o-amino or carbon atoms ranges from 0 to 40, optionally
-hydrazido substituted having halogen or polarizing or water-
formazans), and Poly(o- insolubilizing/solubilizing groups
attached. amino or -hydrazido (Must include ortho-amine or
hydrazide substituted formazans) substituted aryl R derivatives,
and beta- (N--N Bidentates, N--N amine or hydrazide substituted
alkyl R Tridentates, N--N derivatives.) Ligand can also contain
Tetradentates, and N--N nonbinding N, O, S, or P atoms.
Hexadentates) N Valence Stabilizer #41: RR'C.dbd.N--N.dbd.CR"R"' or
RR'C.dbd.N-- Ortho-amino (or NR"R"' (for ketazines), where R, R',
R", -hydrazido) Substituted and R"' represent H, or any organic
Azines (including functional group wherein the number of
ketazines), Bis(o-amino carbon atoms ranges from 0 to 40,
optionally or hydrazido substituted having halogen or polarizing or
water- azines), and Poly(o-amino insolubilizing/solubilizing groups
or hydrazido substituted attached. (Must include ortho-amine or
azines) (N --N Bidentates, hydrazide substituted aryl R
derivatives, and N--N Tridentates, beta-amine or hydrazide
substituted alkyl R N--N Tetradentates, and derivatives.) Ligand
can also contain N--N Hexadentates) nonbinding N, O, S, or P atoms.
N Valence Stabilizer #42: RR'C.dbd.N--R", where R, R', and R"
Schiff Bases with one represent H, or any organic functional group
Imine (C.dbd.N) Group and wherein the number of carbon atoms ranges
with ortho- or alpha- or from 0 to 40, optionally having halogen or
beta-amino or imino or polarizing or water-insolubilizing/ oximo or
diazeno or solubilizing groups attached. (Must contain hydrazido
substitution ortho- or alpha- or beta-amino or imino or (N--N
Bidentates, N--N oximo or diazeno or hydrazido substitution.)
Tridentates, N--N Ligand can also contain nonbinding N, O, S,
Tetradentates, N--N or P atoms. Pentadentates, or N--N
Hexadentates). Also includes hydrazones with ortho-N substitution.
N Valence Stabilizer #43: RR'C.dbd.N--R"--N.dbd.CR"'- R"" or Schiff
Bases with two R--N.dbd.C--R'--CN--R' or Imine (C.dbd.N) Groups
RC.dbd.N--R'--N.dbd.CR", where R, R', R", and without ortho- (for
aryl R"', and R"" represent H, or any organic constituents) or
alpha- functional group wherein the number of or beta- (for alkyl
carbon atoms ranges from 0 to 40, optionally constituents) hydroxy,
having halogen or polarizing or water- carboxy, carbonyl, thiol,
insolubilizing/solubilizing groups attached. mercapto,
thiocarbonyl, (Not including ortho-, alpha-, or beta- amino, imino,
oximo, hydroxy, carboxy, carbonyl, thiol, mercapto, diazeno, or
hydrazido thiocarbonyl, amino, imino, oximo, diazeno, substitution
(N--N or hydrazido substitution.) Ligand can also Bidentates). Also
includes contain nonbinding N, O, S, or P atoms. dihydrazones. N
Valence Stabilizer #44: RR'C.dbd.N--R"--N.dbd.CR"'- R"" or Schiff
Bases with two R--N.dbd.C--R'--C.dbd.N--R' or Imine (C.dbd.N)
Groups and RC.dbd.N--R'--N.dbd.CR", where R, R', R", with ortho- or
alpha- or R"', and R"" represent H, or any organic beta-amino or
imino or functional group wherein the number of oximo or diazeno or
carbon atoms ranges from 0 to 40, optionally hydrazido substitution
having halogen or polarizing or water- (N--N Tridentates,
insolubilizing/solubilizing groups attached. N--N Tetradentates,
(Must contain ortho- or alpha- or beta-amino N--N Pentadentates, or
or imino or oximo or diazeno or hydrazido N--N Hexadentates).
substitution.) Ligand can also contain Also includes hydrazones
nonbinding N, O, S, or P atoms. with ortho-N substitution. N
Valence Stabilizer #45: N(--R--N.dbd.CR'R").sub.3 , where R, R',
and R" Schiff Bases with three represent H, or any organic
functional group Imine (C.dbd.N) Groups and wherein the number of
carbon atoms ranges without ortho- (for aryl from 0 to 40,
optionally having halogen or constituents) or alpha- polarizing or
water-insolubilizing/ or beta- (for alkyl solubilizing groups
attached. (Not including constituents) hydroxy, ortho-, alpha-, or
beta-hydroxy, carboxy, carboxy, carbonyl, thiol, carbonyl, thiol,
mercapto, thiocarbonyl, mercapto, thiocarbonyl, amino, imino,
oximo, diazeno, or hydrazido amino, imino, oximo, substitution.)
Ligand can also contain diazeno, or hydrazido nonbinding N, O, S,
or P atoms. substitution (N--N Tridentates). Also includes
trihydrazones. N Valence Stabilizer #46: N(--R--N.dbd.CR'R").sub.3,
where R, R', and R"
Schiff Bases with three represent H, or any organic functional
group Imine (C.dbd.N) Groups and wherein the number of carbon atoms
ranges with ortho- or alpha- or from 0 to 40, optionally having
halogen or beta-amino or imino or polarizing or
water-insolubilizing/ oximo or diazeno or solubilizing groups
attached. (Must contain hydrazido substitution ortho- or alpha- or
beta-amino or imino or (N--N Tetradentates, oximo or diazeno or
hydrazido substitution.) N--N Pentadentates, Ligand can also
contain nonbinding N, O, S, or N--N Hexadentates) or P atoms. S
Valence Stabilizer #1: Macrocyclic ligands containing two, four,
Macrocyclic, or six thioketone binding sites to valence
Macrobicyclic, and stabilize the central metal ion. Can include
Macropolycyclic other hydrocarbon or ring systems bound to
Oligothioketones this macrocyclic ligand, but they do not
(including Catapinands, coordinate with the stabilized, high
valence Cryptands, Cyclidenes, and metal ion. This ligand and/or
attached, Sepulchrates) wherein all uncoordinating
hydrocarbons/rings may or Binding Sites are composed may not have
halogen or polarizing or of Thioketones (typically
water-insolubilizing/solubilizing groups in the beta position)
(S--S attached. Bidentates, S--S Tetradentates, and S--S
Hexadentates) S Valence Stabilizer #2: Macrocyclic ligands
containing two, four, Macrocyclic, six, or eight 1,1-dithiolene
binding sites to Macrobicyclic, and valence stabilize the central
metal ion. Can Macropolycyclic include other hydrocarbon or ring
systems Dithiolenes (including bound to this macrocyclic ligand,
but they do Catapinands, Cryptands, not coordinate with the
stabilized, high Cyclidenes, and valence metal ion. This ligand
and/or Sepulchrates) wherein all attached, uncoordinating
hydrocarbons/rings Binding Sites are may or may not have halogen or
polarizing composed of alpha, alpha or
water-insolubilizing/solubilizing groups dithiols (meaning two
thiol attached. groups on a single carbon atom in the ring) (S--S
Bidentates, S--S Tetradentates, and S--S Hexadentates) S Valence
Stabilizer #3: RC(.dbd.S)--NR'--C(.dbd.S)-- -R" for dithio-
Dithiolmidodialdehydes, imidodialdehydes, and RC(.dbd.S)--NR'--
Dithiohydrazidodialdehydes NH--C(.dbd.S)--R" for dithiohydrazidodi-
(thioacyl thiohydrazides), aldehydes (thioacyl thiohydrazides),
where R, Bis(dithioimidodi- R', and R" represent H, NH.sub.2, or
any aldehydes), Bis(dithio- organic functional group wherein the
number hydrazidodialdehydes), of carbon atoms ranges from 0 to 40,
Poly(dithioimidodi- optionally having halogen or polarizing or
aldehydes), and Poly(di- water-insolubilizing/sol- ubilizing groups
thiohydrazidodialdehydes) attached. Ligand can also contain
nonbinding (S--S Bidentates, N, O, S, or P atoms. S--S Tridentates,
S--S Tetradentates) S Valence Stabilizer #4:
R--O--C(.dbd.S)--NR'--C(.dbd.S)--O--R" or Dithioimidodicarbonic
R--S--C(.dbd.S)--NR'--C(.dbd.S)--S--R" for acids,
Dithiohydrazidodi- dithioimidodicarbonic acids, and R--O-- carbonic
acids, Bis(dithio- C(.dbd.S)--NR'--NH--C(.dbd.S)--O--R" or
imidodicarbonic acids), R--S--C(.dbd.S)--NR'--NH--C(.dbd.S)--S--
Bis(dithiohydrazidodi- R" for dithiohydrazidodicarbonic acids,
carbonic acids), Poly(di- where R, R', and R"represent H, NH.sub.2,
or thioimidodicarbonic acids), any organic functional group wherein
the Poly(dithiohydrazidodi- number of carbon atoms ranges from 0 to
40, carbonic acids) and optionally having halogen or polarizing or
derivatives thereof water-insolubilizing/solubilizing groups (S--S
Bidentates, attached. Ligand can also contain S--S Tridentates,
nonbinding N, O, S, or P atoms. S--S Tetradentates) S Valence
Stabilizer #5: R--C(.dbd.S)--CR'R"--C(.dbd.S)--R"' where
1,3-Dithioketones (Dithio- R, R', R", and R"' represent H,
NH.sub.2, or beta-ketonates), 1,3,5- any organic functional group
wherein the Trithioketones, Bis(1,3- number of carbon atoms ranges
from 0 to 40, Dithioketones), and optionally having halogen or
polarizing or Poly(1,3-Dithioketones)
water-insolubilizing/solubilizing groups (S--S Bidentates, S--S
attached. Ligand can also contain Tridentates, S--S nonbinding N,
O, S, or P atoms. Tetradentates) S Valence Stabilizer #6:
R--C(.dbd.S)--C(.dbd.S)--R- ' where R and R' 1,2-Dithioketones
represent H, NH.sub.2, or any organic functional (Dithiolenes,
Dithio- group wherein the number of carbon atoms alpha-ketonates),
1,2,3- ranges from 0 to 40, optionally having Trithioketones,
halogen or polarizing or water-insolubilizing/ Dithiotropolonates,
solubilizing groups attached. Ligand can also ortho-Dithioquinones,
contain nonbinding N, O, S, or P atoms. Bis(1,2-Dithioketones), and
Poly(1,2-Dithioketones) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) S Valence Stabilizer #7:
RR'--N--C(.dbd.S)--CR"R"'--C(.dbd.S)--N-- Dithiomalonamides
R""R'""where R, R', R", R"',R"", and R""' (Dithiomalonodiamides),
represent H, NH.sub.2, or any organic functional
Bis(dithiomalonamides), group wherein the number of carbon atoms
and Polydithiomalonamides ranges from 0 to 40, optionally having
(S--S Bidentates, halogen or polarizing or water-insolubilizing/
S--S Tridentates, solubilizing groups attached. Ligand can also
S--S Tetradentates) contain nonbinding N, O, S, or P atoms. S
Valence Stabilizer #8: RR'--N--C(.dbd.S)--CR"R"'--C(.dbd.S)--R""
2-Thioacylthioacetamides, where R, R', R", R"', and R"" represent
H, Bis(2-thioacylthio- NH.sub.2, or any organic functional group
acetamides), and Poly(2- wherein the number of carbon atoms ranges
thioacylthioacetamides) from 0 to 40, optionally having halogen or
(S--S Bidentates, polarizing or water-insolubilizing/ S--S
Tridentates, solubilizing groups attached. Ligand can also S--S
Tetradentates) contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #9: R--C(.dbd.S)--S--C(.dbd.S)--R' where R and
Dithioacyl sulfides, R' represent H or any organic functional
Bis(dithioacyl sulfides), group wherein the number of carbon atoms
and Poly(dithioacyl ranges from 0 to 40, optionally having
sulfides) (S--S halogen or polarizing or water-insolubilizing/
Bidentates, S--S solubilizing groups attached. Ligand can also
Tridentates, S--S contain nonbinding N, O, S, or P atoms.
Tetradentates) S Valence Stabilizer #10: RR'--N--C(.dbd.S)--S--C(.-
dbd.S)--N--R"R"' Trithiodicarbonic Diamides, where R, R', R", and
R"' represent H, NH.sub.2 Bis(trithiodicarbonic or any organic
functional group wherein the diamides), and Poly(tri- number of
carbon atoms ranges from 0 to 40, thiodicarbonic diamides)
optionally having halogen or polarizing or (S--S Bidentates,
water-insolubilizing/solubilizing groups S--S Tridentates,
attached. Ligand can also contain nonbinding S--S Tetradentates) N,
O, S, or P atoms. S Valence Stabilizer #11:
R--S--C(.dbd.S)--S--C(.dbd.S)--S--R' for Pentathio-, Tetrathio-, or
pentathiodicarbonic acids, R--O--C(.dbd.S)-- Trithiodicarbonic
Acids, S--C(.dbd.S)--S--R' for tetrathiodicarbonic Bis(pentathio-,
tetrathio-, acids, and R--O--C(.dbd.S)--S--C(.dbd.S)-- or
trithiodicarbonic acids), O--R' for pentathiodicarbonic acids,
Poly(pentathio-, tetrathio-, where R and R' represent H, NH.sub.2
or any or trithiodicarbonic acids), organic functional group
wherein the number and derivatives thereof of carbon atoms ranges
from 0 to 40, (S--S Bidentates, optionally having halogen or
polarizing or S--S Tridentates, water-insolubilizing/solubilizing
groups S--S Tetradentates) attached. Ligand can also contain
nonbinding N, O, S, or P atoms. S Valence Stabilizer #12:
(R--O--)(R'--O--)P(.dbd.S)--P(.dbd.S) Dithiohypophosphoric
(--O--R")(--O--R"'); (R--O--)(R'--S--) Acids, Bis(dithiohypo-
P(.dbd.S)--P(.dbd.S)(--S--R")(--O--R"'); phosphoric acids), and or
(R--S--)(R'--S--)P(.dbd.S)--P(.dbd.S) Poly(dithiohypophosphoric
(--S--R")(--S--R"'), where R, R', R", and acids), and derivatives
R"' represent H, NH.sub.2 or any organic thereof (S--S Bidentates,
functional group wherein the number of S--S Tridentates, carbon
atoms ranges from 0 to 40, optionally S--S Tetradentates) having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
Note: these ligands are not to be confused with hypophosphorous
acid derivatives (hypophosphites) (R--O--) R"R"'P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. S Valence Stabilizer #13:
(RR'--N--)(R"R"'--N--)P(.dbd.S)(--- N-- Dithiohypophosphoramides,
R""R""')(--N--R"""R"""'), where R, R', Bis(dithiohypophosphor- R",
R"', and R"", R""', R""", and R"""' amides), Poly(dithiohypo-
represent H, NH.sub.2 or any organic functional phosphoramides)
(S--S group wherein the number of carbon atoms Bidentates, S--S
ranges from 0 to 40, optionally having Tridentates, S--S halogen or
polarizing or water-insolubilizing/ Tetradentates) solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. Note: these ligands are not to be confused with
hypophosphorous acid derivatives (hypophosphites)
(R--O--)R"R"'P(.dbd.O) which are very reducing and therefore
unacceptable for stabilization of high valence states in metal
ions. S Valence Stabilizer #14:
(R--O--)(R'--O--)P(.dbd.S)--NH--P(.dbd.S) Dithioimidodiphosphoric
(--O--R")(--O--R"'); (R--O--)(R'--S--) Acids, Dithiohydrazidodi-
P(.dbd.S)--NH--P(.dbd.S )(--S--R")(--O-- phosphoric Acids, Bis(di-
R"'); or (R--S--)(R'--S--)P(.dbd.S)--NH-- thioimidodiphosphoric
P(.dbd.S)(--S--R")(--S--R"') for dithio- Acids), Bis(dithiohydra-
imidodiphosphoric acids, and --NH--NH-- zidodiphosphoric Acids),
derivatives for dithiohydrazidodiphosphoric Poly(dithioimidodi-
acids, where R, R', R", and R"' represent phosphoric Acids),
Poly(di- H, NH.sub.2 or any organic functional group
thiohydrazidodiphosphoric wherein the number of carbon atoms ranges
Acids), and derivatives from 0 to 40, optionally having halogen or
thereof (S--S Bidentates, polarizing or water-insolubilizing/ S--S
Tridentates, solubilizing groups attached. Ligand can also S--S
Tetradentates) contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #15: (RR'--N--)(R"R'"--N--)(.dbd.S)--NH--
Dithioimidodiphosphor- P(.dbd.S)(--N--R""R""')(--N--R"""R"""')
amides, Dithiohydrazidodi- for dithioimidophosphoramides, and
phosphoramides, Bis(di- (RR '--N--)(R"R"'--N--)P(.dbd.S)--NH--
thioimidodiphosphor- NH--P(.dbd.S)(--N--R""R""') amides),
Bis(dithiohydra- (--N--R"""R"""') for dithiohydrazidodi-
zidodiphosphoramides), phosphoramides, where R, R', R", R"', R"",
Poly(dithioimidodiphos- R""', R""", and R"""' represent H, NH.sub.2
or phoramides), and Poly(di- any organic functional group wherein
the thiohydrazidodiphosphor- number of carbon atoms ranges from 0
to 40, amides) (S--S Bidentates, optionally having halogen or
polarizing or S--S Tridentates, water-insolubilizing/solubilizing
groups S--S Tetradentates) attached. Ligand can also contain
nonbinding N, O, S, or P atoms. S Valence Stabilizer #16:
(RR'--N--)(R"R"'--N--)P(.dbd.S)--S--P(.dbd.S)(--N--
Dithiodiphosphoramides, R""R""')(--N--R"""R"""'), or (RR'--N--)
Bis(dithioiphosphor- (R"R"'--N--)P(.dbd.S)--O--P(.dbd.S) amides),
and Poly(dithio- (--N--R"""R"""'), where R, R', R", R"',
diphosphoramides) (S--S R"", R""', R""", and R"""' represent H,
Bidentates, S--S NH.sub.2 or any organic functional group wherein
Tridentates, S--S the number of carbon atoms ranges from 0 to
Tetradentates) 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #17:
(R--O--)(R '--O--)P(.dbd.S)--O-- Dithiodiphosphoric Acids,
P(.dbd.S)(--O--R")(--O--R"'); Bis(dithioiphosphoric (R--O--)(R
'--O--)P(.dbd.S)--S-- Acids), Poly(dithiodiphos-
P(.dbd.S)(--O--R")(--O--R"'); phoric Acids), and (R--O--)(R
'--O--)P(.dbd.S)--O-- derivatives thereof
P(.dbd.S)(--O--R")(--O--R"'); (S--S Bidentates, (R--O--)(R
'--O--)P(.dbd.S)--S-- S--S Tridentates, P(.dbd.S)(--O--R")(--O--R"-
'); or S--S Tetradentates) (R--S--)(R '--O--)P(.dbd.S)--S--
P(.dbd.S)(--O--R")(--O--R"'); where R, R', R", R"', R"", R""',
R""", and R"""'represent H, NH.sub.2 or any organic functional
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #18:
(O.dbd.)P(--S--R)(--S--R')(--S--R") or Trithiophosphoric Acids
(S.dbd.)P(--S--R)(--S--R')(--O--R"), (Phosphorotrithioic Acids),
where R, R', and R" represent H, NH.sub.2 or any
Bis(trithiophosphoric organic functional group wherein the number
acids), Poly(trithiophos- of carbon atoms ranges from 0 to 40,
phoric acids), and optionally having halogen or polarizing or
derivatives thereof water-insolubilizing/solubilizing groups (S--S
Bidentates, attached. Ligand can also contain S--S Tridentates,
nonbinding N, O, S, or P atoms. S--S Tetradentates) S Valence
Stabilizer #19: (O.dbd.)P(--S--R)(--S--R')(--O--R") or
Dithiophosphoric Acids (S.dbd.)P(--S--R)(--O--R')(--O--R"),
(Phosphorodithioic Acids), where R, R', and R"represent H, NH.sub.2
or any Bis(dithiophosphoric acids), organic functional group
wherein the number Poly(dithiophosphoric of carbon atoms ranges
from 0 to 40, acids), and derivatives optionally having halogen or
polarizing or thereof (S--S Bidentates, water-insolubilizing/solub-
ilizing groups S--S Tridentates, attached. Ligand can also contain
nonbinding S--S Tetradentates) N, O, S, or P atoms. S Valence
Stabilizer #20: (S.dbd.)P(--S--R)(--S--R')(--S--R"), where
Tetrathiophosphoric Acids R, R', and R" represent H, NH.sub.2 or
any (Phosphorotetrathioic organic functional group wherein the
number Acids), Bis(tetrathio- of carbon atoms ranges from 0 to 40,
phosphoric acids), optionally having halogen or polarizing or
Poly(tetrathiophosphoric water-insolubilizing/solubilizing groups
acids), and derivatives attached. Ligand can also contain
nonbinding thereof (S--S Bidentates, N, O, S, or P atoms. S--S
Tridentates, S--S Tetradentates) S Valence Stabilizer #21:
(O.dbd.)P(--S--S--R)(--S--R')(--S--R") or Phosphoro(dithioperoxo)d-
i- (S)P(--S--S--R)(--S--R')(--O--R"), thioic Acids, Bis[phos- where
R, R', and R"represent H, NH.sub.2 or any phoro(dithioperoxo)dithi-
oic organic functional group wherein the number Acids],
Poly[phosphoro(di- of carbon atoms ranges from 0 to 40,
thioperoxo)dithioic Acids], optionally having halogen or polarizing
or and derivatives thereof water-insolubilizing/solubilizing groups
(S--S Bidentates, attached. Ligand can also contain nonbinding S--S
Tridentates, N, O, S, or P atoms. S--S Tetradentates) S Valence
Stabilizer #22: (O.dbd.)P(--S--S--R)(--S--R')(--O--R") or
Phosphoro(dithio- (S.dbd.)P(--S--S--R)(--O--R')(--O--R"),
peroxo)thioic Acids, where R, R', and R"represent H, NH.sub.2 or
any Bis[phosphoro(dithio- organic functional group wherein the
number peroxo)thioic Acids], of carbon atoms ranges from 0 to 40,
Poly[phosphoro(dithio- optionally having halogen or polarizing or
peroxo)thioic Acids], water-insolubilizing/solubilizing groups and
derivatives thereof attached. Ligand can also contain nonbinding
(S--S Bidentates, N, O, S, or P atoms. S--S Tridentates, S--S
Tetradentates) S Valence Stabilizer #23:
(S.dbd.)P(--S--S--R)(--S--R')(--S--R"), Phosphoro(dithioper- where
R, R', and R" represent H, NH.sub.2 or any oxo)trithioic Acids,
organic functional group wherein the number Bis[phosphoro(dithio-
of carbon atoms ranges from 0 to 40, peroxo)trithioic Acids],
optionally having halogen or polarizing or Poly[phosphoro(dithio-
water-insolubilizing/solubilizing groups peroxo)trithioic
Acids],
attached. Ligand can also contain nonbinding and derivatives
thereof N, O, S, or P atoms. (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) S Valence Stabilizer #24:
R--CR'(--SH)--CH.sub.2--C(.dbd.S)--R", where
Beta-Mercaptothioketones, R, R', and R" represent H, NH.sub.2 or
any Beta-Mercaptothio- organic functional group wherein the number
aldehydes, Bis(beta- of carbon atoms ranges from 0 to 40,
mercaptothioketones), optionally having halogen or polarizing or
Bis(beta-mercaptothio- water-insolubilizing/solubilizing groups
aldehydes), Poly(beta- attached. Ligand can also contain nonbinding
mercaptothioketones), N, O, S, or P atoms. and Poly(beta-
mercaptothioaldehydes) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) S Valence Stabilizer #25:
RR'--N--CH(--SH)--NR"--C(.dbd.S)-- N-(Aminomethylthiol)thio-
NR"'R"", where R, R', R", R"', and R"" ureas [N-(Aminomercapto-
represent H, NH.sub.2 or any organic functional methyl)thioureas],
Bis[N- group wherein the number of carbon atoms
(aminomethylthiol)thio- ranges from 0 to 40, optionally having
ureas], and Poly[N-(amino- halogen or polarizing or
water-insolubilizing/ methylthiol)thioureas] solubilizing groups
attached. Ligand can also (S--S Bidentates, contain nonbinding N,
O, S, or P atoms. S--S Tridentates, S--S Tetradentates) S Valence
Stabilizer #26: RR'--N--C(.dbd.S)--C(.dbd.S)--N--R"R"',
Dithiooxamides, where R, R', and R", and R"' represent H,
Bis(dithiooxamides), NH.sub.2 or any organic functional group
wherein Poly(dithiooxamides) the number of carbon atoms ranges from
0 (S--S Bidentates, to 40, optionally having halogen or S--S
Tridentates, polarizing or water-insolubilizing/ S--S
Tetradentates) solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #27:
RR'--C.dbd.C(--S.sup.-)(--S.sup.-), where R and R' 1,1-Dithiolates,
Bis(1,1- represent H, NH.sub.2 or any organic functional
dithiolates), and group wherein the number of carbon atoms
Poly(1,1-dithiolates) ranges from 0 to 40, optionally having (S--S
Bidentates and halogen or polarizing or water-insolubilizing/ S--S
Tetradentates) solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #28:
R--C(.dbd.S)(--S--R') for dithiomono- Dithiomonocarboxylic
carboxylic acids, and (R--S--)(S.dbd.)C-- Acids, Tri- and
Tetrathio- R'--C(.dbd.S)(--S--R") for tri- and tetra- dicarboxylic
Acids, thiodicarboxylic acids, where R, R', and R"
Bis(dithiomonocarboxylic represent H, NH.sub.2 or any organic
functional Acids), Bis(tri- and tetra- group wherein the number of
carbon atoms thiodicarboxylic acids), ranges from 0 to 40,
optionally having Poly(dithiomonocarboxylic halogen and or
polarizing or water- acids), Poly(tri- and
insolubilizing/solubilizing groups attached. tetrathiodicarboxylic
Ligand can also contain nonbinding N, O, S, acids), derivatives
thereof or P atoms. (S--S Bidentates and S--S Tetradentates) S
Valence Stabilizer #29: R--C(.dbd.S)(--S--S--R') for perthiomono-
Perthiomonocarboxylic carboxylic acids, and (R--S--S--)(S.dbd.)C--
Acids, Perthiodicarboxylic R'--C(.dbd.S)(--S--S--R") for perthiodi-
Acids, Bis(perthiomono- carboxylic acids, where R, R', and R"
carboxylic acids), represent H, NH.sub.2 or any organic functional
Bis(perthiodicarboxylic group wherein the number of carbon atoms
acids), Poly(perthiomono- ranges from 0 to 40, optionally having
carboxylic acids), halogen or polarizing or water-
Poly(perthiodicarboxylic insolubilizing/solubilizing groups
attached. acids), and derivatives Ligand can also contain
nonbinding N, O, S, thereof (S--S Bidentates or P atoms. and S--S
Tetradentates) S Valence Stabilizer #30: R--S--C(.dbd.S)--O--R' or
Dithiocarbonates, R--S--C(.dbd.O)--S--R' for dithiocarbonates,
Trithiocarbonates, R--S--C(.dbd.S)--S--R' for trithiocarbonates,
Perthiocarbonates, and R--S--S--C(.dbd.S)--S--R' for perthio-
Bis(dithiocarbonates), carbonates, where R, and R' represent H,
Bis(trithiocarbonates), and NH.sub.2 or any organic functional
group wherein Bis(perthiocarbonates) the number of carbon atoms
ranges from 0 to (S--S Bidentates and 40, optionally having halogen
or polarizing S--S Tetradentates) or
water-insolubilizing/solubilizin- g groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer
#31: RR'N.sup.+ .dbd.C(SH)(SH), where R and R' represent
Dithiocarbamates, H, OH, SH, OR" (R".dbd.C.sub.1-C.sub.30 alkyl or
Bis(dithiocarbamates), aryl), SR" (R".dbd.C.sub.1-C.sub.30 alkyl or
aryl), and Poly(dithiocarbamates) NH.sub.2 or any organic
functional group wherein (including N-hydroxydi- the number of
carbon atoms ranges from 0 to thiocarbamates and N- 40, optionally
having halogen or polarizing mercaptodithiocarbamates) or
water-insolubilizing/solubilizing groups (S--S Bidentates,
attached. Ligand can also contain nonbinding S--S Tridentates, and
N, O, S, or P atoms. S--S Tetradentates) S Valence Stabilizer #32:
RR'N--NR"--C(.dbd.S)(SH), where R and R' Dithiocarbazates represent
H, NH.sub.2 or any organic functional (Dithiocarbazides), group
wherein the number of carbon atoms Bis(dithiocarbazates), and
ranges from 0 to 40, optionally having Poly(dithiocarbazates)
halogen or polarizing or water- (S--S Bidentates,
insolubilizing/solubilizing groups S--S Tridentates, and attached.
Ligand can also contain nonbinding S--S Tetradentates; or N, O, S,
or P atoms. possibly N--S Bidentates, N--S Tridentates, and N--S
Tetradentates) S Valence Stabilizer #33: Thiocyanates bound
directly to the high Thiocyanate ligands valence metal ion. (S
Monodentates) O Valence Stabilizer #1:
RR'--N--C(.dbd.O)--NR"--C(.dbd.O)-- Biurets (Imidodicarbonic
NR"'R"" for biurets, and RR'--N-- Diamides), Isobiurets,
C(.dbd.O)--NR"--NH--C(.dbd.O)--NR"'R"" Biureas, Triurets, for
biureas, where R, R', R", R"', and R'"' Triureas, Bis(biurets),
represent H, NH.sub.2, or any organic functional Bis(isobiurets),
group wherein the number of carbon atoms Bis(biureas),
Poly(biurets), ranges from 0 to 40, optionally having
Poly(isobiurets), halogen or polarizing or water- and Poly(biureas)
insolubilizing/solubilizing groups (O--O Bidentates, attached.
Ligand can also contain nonbinding O--O Tridentates, N, O, S, or P
atoms. O--O Tetradentates) O Valence Stabilizer #2:
RR'--N--C(.dbd.O)--NR"--C(.dbd.O)--R"' Acylureas, Aroylureas, where
R, R', R", and R"' represent H, NH.sub.2, Bis(acylureas), or any
organic functional group wherein the Bis(aroylureas), number of
carbon atoms ranges from 0 to 40, Poly(acylureas), and optionally
having halogen or polarizing or Poly(aroylureas)
water-insolubilizing/solubilizing groups (O--O Bidentates,
attached. Ligand can also contain nonbinding O--O Tridentates, N,
O, S, or P atoms. O--O Tetradentates) O Valence Stabilizer #3:
RC(.dbd.O)--NR'--C(.dbd.O)--R" for Imidodialdehydes,
imidodialdehydes, and RC(.dbd.O)--NR -- Hydrazidodialdehydes
NH--C(.dbd.O)--R" for hydrazidodialdehydes (Acyl hydrazides), (acyl
hydrazides), where R, R', and R" Bis(imidodialdehydes), represent
H, NH.sub.2, or any organic functional Bis(hydrazidodialdehydes),
group wherein the number of carbon atoms Poly(imidodialdehydes),
ranges from 0 to 40, optionally having and Poly(hydrazidodi-
halogen or polarizing or water- aldehydes) (O--O
insolubilizing/solubilizing groups attached. Bidentates, O--O
Ligand can also contain nonbinding N, O, S, Tridentates, O--O or P
atoms. Tetradentates) O Valence Stabilizer #4:
R--O--C(.dbd.O)--NR'--C(.dbd.O)--O--R" for Imidodicarbonic acids,
imidodicarbonic acids, and R--O-- Hydrazidodicarbonic acids,
C(.dbd.O)--NR'--NH--C(.dbd.O)--O--R" for Bis(imidodicarbonic
acids), hydrazidodicarbonic acids, where R, R', and
Bis(hydrazidodicarbonic R" represent H, NH.sub.2, or any organic
acids), Poly(imidodi- functional group wherein the number of
carbonic acids), carbon atoms ranges from 0 to 40, optionally
Poly(hydrazidodicarbonic having halogen or polarizing or water-
acids) and derivatives insolubilizing/solubilizing groups attached.
thereof (O--O Bidentates, Ligand can also contain nonbinding N, O,
S, O--O Tridentates, or P atoms. O--O Tetradentates) O Valence
Stabilizer #5: RR'--N--S(.dbd.O)(.dbd.O)--NR"-- Imidodisulfamic
Acid, S(.dbd.O)(.dbd.O)--NR'"R"" for imidodisulfamic
Imidodisulfuric Acid, acid, and R--O--S(.dbd.O)(.dbd.O)--NR'--
Bis(Imidodisulfamic Acid), S(.dbd.O)(.dbd.O)--OR" for imidosulfuric
acid, Bis(Imidodisulfuric Acid), where R, R', and R" represent H,
NH.sub.2, or Poly(Imidodisulfamic any organic functional group
wherein the Acid), and Poly(Imido- number of carbon atoms ranges
from 0 to 40, disulfuric Acid) and optionally having halogen or
polarizing or derivatives thereof water-insolubilizing/solubilizin-
g groups (O--O Bidentates, attached. Ligand can also contain
nonbinding O--O Tridentates, N, O, S, or P atoms. O--O
Tetradentates) O Valence Stabilizer #6: R--C(.dbd.O)--CR'R"--C(.db-
d.O)--R"' where 1,3-Diketones (Beta- R, R', R", and R"' represent
H, NH.sub.2, or any Diketonates), 1,3,5- organic functional group
wherein the number Triketones, Bis(1,3- of carbon atoms ranges from
0 to 40, Diketones), and Poly(1,3- optionally having halogen or
polarizing or Diketones), all with a water-insolubilizing/solub-
ilizing groups Molecular Weight Greater attached. Ligand can also
contain nonbinding than 125 (O--O Bidentates, N, O, S, or P atoms.
If these ligands exhibit O--O Tridentates, a molecular weight less
than or equal to 125, O--O Tetradentates) the solubility of the
resultant Mn.sup.+3- diketonate complex will be too high. O Valence
Stabilizer #7: R--C(.dbd.O)--C(.dbd.O)--R' where R and R'
1,2-Diketones (Alpha- represent H, NH.sub.2, or any organic
functional Diketonates), 1,2,3- group wherein the number of carbon
atoms Triketones, Tropolonates, ranges from 0 to 40, optionally
having ortho-Quinones, halogen or polarizing or
water-insolubilizing/ Bis(1,2-Diketones), and solubilizing groups
attached. Ligand can also Poly(1,2-Diketones), all contain
nonbinding N, O, S, or P atoms. If with a Molecular Weight these
ligands exhibit a molecular weight less Greater than 100 than or
equal to 100, the solubility of the (O--O Bidentates, resultant
Mn.sup.+3-diketonate complex will be O--O Tridentates, too high.
O--O Tetradentates) O Valence Stabilizer #8:
RR'--N--C(.dbd.)--CR"R"'--C(.dbd.O)--N-- Malonamides R""R""' where
R, R', R", R"',R"", and R""' (Malonodiamides), represent H,
NH.sub.2, or any organic functional Bis(malonamides), and group
wherein the number of carbon atoms Polymalonamides ranges from 0 to
40, optionally having (O--O Bidentates, halogen or polarizing or
water- O--O Tridentates, insolubilizing/solubilizing groups
attached. O--O Tetradentates) Ligand can also contain nonbinding N,
O, S, or P atoms. O Valence Stabilizer #9:
RR'--N--C(.dbd.O)--CR"R"'--C(.dbd.O)--R"" 2-Acylacetamides, where
R, R', R", R"', and R"" represent H, Bis(2-acylacetamides),
NH.sub.2, or any organic functional group and
Poly(2-acylacetamides) wherein the number of carbon atoms ranges
(O--O Bidentates, from 0 to 40, optionally having halogen or O--O
Tridentates, polarizing or water-insolubilizing/ O--O
Tetradentates) solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #10:
RR'--N--C(.dbd.O)--S--C(.dbd.O)--N--R"R"' Monothiodicarbonic where
R, R', R", and R"' represent H, NH.sub.2 or Diamides, any organic
functional group wherein the Bis(monothiodicarbonic number of
carbon atoms ranges from 0 to 40, diamides), and optionally having
halogen or polarizing or Poly(monothiodicarbonic
water-insolubilizing/solubilizing groups diamides) (O--O attached.
Ligand can also contain nonbinding Bidentates, O--O N, O, S, or P
atoms. Tridentates, O--O Tetradentates) O Valence Stabilizer #11:
R--O--C(.dbd.O)--S--C(.dbd.O)--O--R', Monothiodicarbonic Acids,
where R and R' represent H, NH.sub.2 or any Bis(monothiodicarbonic
organic functional group wherein the number acids),
Poly(monothiodi- of carbon atoms ranges from 0 to 40, carbonic
acids), and optionally having halogen or polarizing or derivatives
thereof water-insolubilizing/solubilizing groups (O--O Bidentates,
attached. Ligand can also contain nonbinding O--O Tridentates, N,
O, S, or P atoms. O--O Tetradentates) O Valence Stabilizer #12:
R--O--S(.dbd.O)(.dbd.O)--S--S(.dbd.O)--O--R' Trithionic acid, where
R and R' represent H, NH.sub.2 or any Bis(trithionic acid), organic
and derivatives functional group wherein the Poly(trithionic acid),
number of carbon atoms ranges from 0 to 40, thereof (O--O
Bidentates, optionally having halogen or polarizing or O--O
Tridentates, water-insolubilizing/solubilizing groups O--O
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. O Valence Stabilizer #13:
(R--O--)(R'--O--)P(.dbd.O)-- Hypophosphoric Acids, P(.dbd.O)
(--O--R")(--O--R'"), where R, Bis(hypophosphoric acids), R', R",
and R"' represent H, NH.sub.2 or any and Poly(hypophosphoric
organic functional group wherein the number acids), and derivatives
of carbon atoms ranges from 0 to 40, thereof (O--O Bidentates,
optionally having halogen or polarizing or O--O Tridentates,
water-insolubilizing/solubilizing groups O--O Tetradentates)
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
Note: these ligands are not to be confused with hypophosphorous
acid derivatives (hypophosphites) (R--O--)R"R"'P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. O Valence Stabilizer #14:
(RR'--N--)(RR"R'"--N--)P(.db- d.O)-- Hypophosphoramides,
P(.dbd.O)(--N--R""R""')(--N--R"""R"""'), Bis(hypophosphoramides),
where R, R', R", R"', R"", R""', R""", and and Poly(hypophosphor-
R"""'represent H, NH.sub.2 or any organic amides) (Q--O Bidentates,
functional group wherein the number of O--O Tridentates, carbon
atoms ranges from 0 to 40, optionally O--O Tetradentates) having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
Note: these ligands are not to be confused with hypophosphorous
acid derivatives (hypophosphites) (R--O--)R"R"'P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. O Valence Stabilizer #15:
(R--O--)(R'--O--)P(.dbd.O)--NH-- Imidodiphosphoric Acids,
P(.dbd.O)(--O--R")(--O)--R"') for Hydrazidodiphosphoric
imidodiphosphoric acids, and (R--O--)(R'-- Acids, Bis(imidodiphos-
O--)P(.dbd.O)--NH--NH--P(.dbd.O)(--O--R") phoric Acids), Bis(hydra-
(--O--R"') for hydrazidodiphosphoric zidodiphosphoric Acids),
acids; where R, R', R", and R"' represent H, Poly(imidodiphosphoric
NH.sub.2 or any organic functional group Acids), Poly(hydra-
wherein the number of carbon atoms ranges zidodiphosphoric Acids),
from 0 to 40, optionally having halogen or and derivatives thereof
polarizing or water-insolubilizing/ (O--O Bidentates, solubilizing
groups attached. Ligand can also O--O Tridentates, contain
nonbinding N, O, S, or P atoms. O--O Tetradentates) O Valence
Stabilizer #16: (RR'--N--)(R"R"'--N--)P(.- dbd.O)--NH--
Imidodiphosphoramides, P(.dbd.O)(--N--R""R""')(--N--R"- ""R"""')
Hydrazidodiphos- for imidodiphosphoramides, and phoramides,
Bis(imidodi- --NH--NH-- derivatives for hydrazidodi-
phosphoramides), phosphoramides, where R, R', R", R"', R"",
Bis(hydrazidodi- R""', R"'"', and R"""' represent H, NH.sub.2 or
phosphoramides), any organic functional group wherein the
Poly(imidodiphos- number of carbon atoms ranges from 0 to 40,
phoramides), and optionally having halogen or polarizing or
Poly(hydrazidodi- water-insolubilizing/solubilizing groups
phosphoramides) attached. Ligand can also contain nonbinding (O--O
Bidentates, N, O, S, or P atoms. O--O Tridentates, O--O
Tetradentates) O Valence Stabilizer #17: (RR'--N--)(R"R"'--N--)PQ.-
dbd.O)--O-- Diphosphoramides,
P(.dbd.O)(--N--R""R""')(--N--R"""R"""- '), Bis(diphosphoramides),
and where R, R', R", R"', R"", R""', R""", and
Poly(diphosphoramides) R"""' represent H, NH.sub.2 or any organic
(O--O Bidentates, functional group wherein the number of O--O
Tridentates, carbon atoms ranges from 0 to 40, optionally O--O
Tetradentates) having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #18:
R--CR'(--OH)--CH2--C(.dbd.O)--R", Beta-Hydroxyketones, where R, R',
and R" represent H, NH.sub.2 or Beta-Hydroxyaldehydes, any organic
functional group wherein the Bis(beta-hydroxyketones), number of
carbon atoms ranges from 0 to 40, Bis(beta- optionally having
halogen or polarizing or hydroxyaldehydes),
water-insolubilizing/solubilizing groups Poly(beta-hydroxyketones),
attached. Ligand can also contain nonbinding and Poly(beta- N, O,
S, or P atoms. hydroxyaldehydes) (O--O Bidentates, O--O
Tridentates, O--O Tetradentates) O Valence Stabilizer #19:
RR'--N--CH(--OH)--NR"--C(.dbd.O)-- N-(Aminomethylol)ureas NR"'R"",
where R, R', R", R"', and R"" [N-(Aminohydroxy- represent H,
NH.sub.2 or any organic functional methyl)ureas], Bis[N- group
wherein the number of carbon atoms (aminomethylol)ureas], ranges
from 0 to 40, optionally having and Poly[N-(amino- halogen or
polarizing or water-insolubilizing/ methylol)ureas] solubilizing
groups attached. Ligand can also (O--O Bidentates, contain
nonbinding N, O, S, or P atoms. O--O Tridentates, O--O
Tetradentates) O Valence Stabilizer #20:
RR'--N--C(.dbd.O)--C(.dbd.O)--N--R"R"', Oxamides, Bis(oxamides),
where R, R', R", and R"' represent H, NH.sub.2 or and
Poly(oxamides) any organic functional group wherein the (O--O
Bidentates, number of carbon atoms ranges from 0 to 40, O--O
Tridentates, optionally having halogen or polarizing or O--O
Tetradentates) water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #21: --C(--OH).dbd.C(--OH)--, where the two Squaric
Acids and carbon atoms supporting the hydroxy groups derivatives
thereof are included within a cyclic hydrocarbon (O--O Bidentates)
moiety, optionally having halogen or polarizing or
water-insolubilizing/ solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #22:
(R--O--)(O.dbd.)C--R'--C(.dbd.O)(--O--R"), Dicarboxylic Acids,
where R, R',and R" represent H, NH.sub.2 or Bis(dicarboxylic
acids), any organic functional group wherein the Poly(dicarboxylic
acids), number of carbon atoms ranges from 0 to 40, and derivatives
thereof optionally having halogen or polarizing or (O--O Bidentates
and water-insolubilizing/solubilizing groups O--O Tetradentates)
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #23: RR'N.sup.+.dbd.C(OH)(OH), where R and R'
Carbamates, represent H, OH, SH, OR" (R".dbd.C.sub.1-C.sub.30
Bis(carbamates), and alkyl or aryl), SR" (R".dbd.C.sub.1-C.sub.30
alkyl Poly(carbamates) or aryl), NH.sub.2 or any organic functional
(including N- group wherein the number of carbon atoms
hydroxycarbamates and ranges from 0 to 40, optionally having
N-mercaptocarbamates) halogen or polarizing or
water-insolubilizing/ (O--O Bidentates, solubilizing groups
attached. Ligand can also O--O Tridentates, and contain nonbinding
N, O, S, or P atoms. O--O Tetradentates) O Valence Stabilizer #24:
RN.dbd.C(OH)(OH), where R represents H, Carbimates, NH.sub.2 or any
organic functional group wherein Bis(carbimates), and the number of
carbon atoms ranges from 0 to Poly(carbimates) 40, optionally
having halogen or polarizing (O--O Bidentates, or
water-insolubilizing/solubilizing groups O--O Tridentates, an
attached. Ligand can also contain nonbinding O--O Tetradentates) N,
O, S, or P atoms. O Valence Stabilizer #25: Cyanates bound directly
to the high valence Cyanate ligands metal ion. (O Monodentates)
N--S Valence RR'--N--C(.dbd.NH)--S--S- --C(.dbd.NH)-- Stabilizer
#1: NR"R"', where R, R', R", and R"' represent Diformamidine
Disulfides H, NH.sub.2, or any organic functional group
(Thioperoxydicarbonimidic wherein the number of carbon atoms ranges
Diamides or Dihydrazides), from 0 to 40, optionally having halogen
or Thioperoxytricarbonimidic polarizing or water-insolubilizing/
Diamides or Dihydrazides, solubilizing groups attached. Ligand can
also Thioperoxytetra- contain nonbinding N, O, S, or P atoms.
carbonimidic Diamides or Dihydrazides, Bis(diformamidine
disulfides), and Poly(diformamidine disulfides) (N--S Bidentates,
N--S Tridentates, N--S Tetradentates) N--S Valence
RR'--N--C(.dbd.NH)--S--CS--NR"R"', Stabilizer #2: where R, R', R",
and R"' represent H, NH.sub.2 or S-Amidinodithio- any organic
functional group wherein the carbamates, Bis(S-amidino- number of
carbon atoms ranges from 0 to 40, dithiocarbamates), and optionally
having halogen or polarizing or Poly(S- amidinodithio-
water-insolubilizing/solubilizing groups carbamates) (N--S
attached. Ligand can also contain nonbinding Bidentates and N, O,
S, or P atoms. N--S Tetradentates) N--S Valence
RR'--N--C(.dbd.NH)--O--CS--NR"R"', Stabilizer #3: where R, R', R",
and R"' represent H, NH.sub.2 or O-Amidinothiocarbamates, any
organic functional group wherein the Bis(O-amidinothio- number of
carbon atoms ranges from 0 to 40, carbamates), and Poly(O-
optionally having halogen or polarizing or amidinothiocarbamates)
water-insolubilizing/solubilizing groups (N--S Bidentates and
attached. Ligand can also contain nonbinding N--S Tetradentates) N,
O, S, or P atoms. N--S Valence RR'--N--C(.dbd.NH)--S--S--CS--NR-
"R"', Stabilizer #4: where R, R', R", and R"' represent H, NH.sub.2
or S-Amidinoperoxythio- any organic functional group wherein the
carbamates, Bis(S-amidino- number of carbon atoms ranges from 0 to
40, peroxythiocarbamates), and optionally having halogen or
polarizing or Poly(S-amidinoperoxythio- water-insolubilizing/solub-
ilizing groups carbamates) (N--S attached. Ligand can also contain
nonbinding Bidentates and N--S N, O, S, or P atoms. Tetradentates)
N--S Valence (NH.dbd.)P(--SR)(--OR')(--OR") for Stabilizer #5:
phosphorimidothioic acid, (NH.dbd.)P(.dbd.SR) Phosphorimidothioic
Acid; (.dbd.SR')(OR") for phosphorimidodithioic
Phosphorimidodithioic acid, (NH.dbd.)P(--SR)(--SR')(--SR") for
Acid; Phosphorimidotri- phosphorimidotrithioic acid, where R, R',
thiole Acid; Bis(Phos- and R" represent H, NH.sub.2 or any organic
phorimidothioic Acid); functional group wherein the number of
Bis(Phosphorimidodithioic carbon atoms ranges from 0 to 40,
optionally Acid); Bis(Phosphorimido- having halogen or polarizing
or water- trithioic Acid); Poly(Phos- insolubilizing/solubilizing
groups attached. phorimidothioic Acid); Ligand can also contain
nonbinding N, Poly(Phosphorimidodithioic O, S, or P atoms. Acid);
Poly(Phosphor- imidotrithioic Acid); and derivatives thereof (N--S
Bidentates and N--S Tetradentates) N--S Valence
(S.dbd.)P(--NRR')(--NR"R"')(--NR""R""'), Stabilizer #6: where R,
R', R", R"', R"", and R""' represent Phosphorothioic Triamides, H,
NH.sub.2 or any organic functional group Bis(phosphorothioic
wherein the number of carbon atoms ranges triamides), and
Poly(phos- from 0 to 40, optionally having halogen or phorothioic
triamides) polarizing or water-insolubilizing/ (N--S Bidentates
solubilizing groups attached. Ligand can also and N--S
Tetradentates) contain nonbinding N, O, S, or P atoms. N--S Valence
(S.dbd.)P(--NRR')(--SR")(--SR"') for Stabilizer #7:
phosphoramidotrithioic acid, and Phosphoramidotrithioic
(S.dbd.)P(--NRR ')(--NR"R"')(--SR"") for Acid, Phosphorodiamido-
phosphorodiamidodithioic acid, where R, R', dithioic Acid, R", R"',
and R""represent H, NH.sub.2 or any Bis(phosphoramido- organic
functional group wherein the number trithioic acid), of carbon
atoms ranges from 0 to 40, Bis(phosphorodiamido- optionally having
halogen or polarizing or dithioic acid),
water-insolubilizing/solubilizing groups poly(phosphoramido-
attached. Ligand can also contain nonbinding trithioic acid), N, O,
S, or P atoms. poly(phosphorodiamido- dithioic acid), and
derivatives thereof (N--S Bidentates and N--S Tetradentates) N--S
Valence (O.dbd.)P(--NRR')(--SR")(--OR"') or Stabilizer #8:
(S.dbd.)P(--NRR')(--OR")(--OR"') for Phosphoramidothioic Acid,
phosphoramidothioic acid; Phosphoramidodithioic
(O.dbd.)P(--NRR')(--SR")(--SR"') or Acid, Phosphorodi-
(S.dbd.)P(--NRR')(--SR")(--OR"') for amidothioic Acid,
phosphoramidodithioic acid; Bis(Phosphoramido-
(O.dbd.)P(--NRR'NR"R"')(--SR"") or thioic Acid),
(S.dbd.)P(--NRR')(--NR"R"')(--OR"") for Bis(Phosphoramido-
phosphorodiamidothioic acid, where R, R', dithioic Acid), R", R"',
and R""represent H, NH.sub.2 or any Bis(Phosphorodi- organic
functional group wherein the number amidothioic Acid), of carbon
atoms ranges from 0 to 40, Poly(Phosphoramido- optionally having
halogen or polarizing or thioic Acid), water-insolubilizing/solubi-
lizing groups Poly(Phosphoramido- attached. Ligand can also contain
nonbinding dithioic Acid), and N, O, S, or P atoms.
Poly(Phosphorodi- amidothioic Acid) (N--S Bidentates and N--S
Tetradentates) N--S Valence R'--C(.dbd.S)--N.dbd.C(--R)(-- -NHR"),
where Stabilizer #9: R is an aromatic derivative (i.e.
--C.sub.6H.sub.5), N-Thioacyl and R'and R" represent H, NH.sub.2,
or any 7-Aminobenzylidenimines organic functional group wherein the
number (N--S Bidentates or of carbon atoms ranges from 0 to 40,
N--S Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence
R--C(.dbd.S)--NR'--OH or Stabilizer #10: R--C(--SH).dbd.N--OH,
where R and R' Thiohydroxamates represent H, NH.sub.2, or any
organic functional (Thiohydroxylamines), group wherein the number
of carbon atoms Bis(thiohydroxamates), and ranges from 0 to 40,
optionally having Poly(thiohydroxamates) halogen or polarizing or
water-insolubilizing/ (N--S Bidentates, solubilizing groups
attached. Ligand can also N--S Tetradentates, contain nonbinding N,
O, S, or P atoms. and N--S Hexadentates) N--S Valence
R--CH(--NHR')--C(.dbd.S)(--OH) or Stabilizer #11:
R--CH(--NHR')--C(.dbd.5)(--SH) for Alpha- or ortho-
aminothiocarboxylic acids, and Aminothiocarboxylic
(HO--)(S.dbd.)C--CH(--NHR)--R'--CH(-- Acids, and alpha- or ortho-
NHR")--C(.dbd.S)(--OH) or (HS--)(S.dbd.)C-- Aminothiodicarboxylic
CH(--NHR)--R'--CH(--NHR")-- Acids, and derivatives C(.dbd.S)(--SH)
for aminothiodicarboxylic thereof (N--S Bidentates, acids, where R,
R', and R"represent any N--S Tridentates, organic functional group
wherein the and N--S Tetradentates) number of carbon atoms ranges
from 1 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence
RR'--N--C(.dbd.S)--NR"--N.dbd.CR"'R"", Stabilizer #12: where R, R',
R", R"', and R"" represent H, Thiosemicarbazones, or any organic
functional group wherein the Bis(thiosemicarbazones), number of
carbon atoms ranges from 0 to 40, and Poly(thiosemi- optionally
having halogen or polarizing or carbazones) (N--S
water-insolubilizing/solubilizing groups Bidentates, N--S attached.
Ligand can also contain nonbinding Tetradentates, and N, O, S, or P
atoms. N--S Hexadentates) N--S Valence
R--C(.dbd.S)--NR'--N.dbd.CR"R"', where R, Stabilizer #13: R', R",
and R"' represent H, or any organic Thioacyl hydrazones, functional
group wherein the number of Bis(thioacyl hydrazones), carbon atoms
ranges from 0 to 40, optionally and Poly(thioacyl having halogen or
polarizing or water- hydrazones) insolubilizing/solubilizing groups
attached. (N--S Bidentates, Ligand can also contain nonbinding N,
O, N--S Tetradentates, S, or P atoms. and N--S Hexadentates) N--S
Valence R--N.dbd.N--C(.dbd.S)--NR'--NR"R"', where Stabilizer #14:
R, R', R", R"' represent H, or any organic Thiocarbazones
functional group wherein the number of (Diazenecarbothioic and
carbon atoms ranges from 0 to 40, optionally hydrazides), having
halogen or polarizing or water- Bis(thiocarbazones), and
insolubilizing/solubilizing groups attached. Poly(thiocarbazones)
Ligand can also contain nonbinding N, O, (N--S Bidentates, S, or P
atoms. N--S Tetradentates, and N--S Hexadentates) N--S Valence
R--N.dbd.N--R' for azo compounds, Stabilizer #15:
R--N.dbd.N--NH--R' for triazenes, where R, Azo compounds including
and R' represent H or any organic functional triazenes with thiol
or group wherein the number of carbon atoms mercapto or
thiocarbonyl ranges from 0 to 40, optionally having substitution at
the ortho- halogen or polarizing or water-insolubilizing/ (for
aryl) or alpha- or beta- solubilizing groups attached. (Must
include (for alkyl) positions, ortho-thio, mercapto, or
thiocarbonyl Bis[o-(HS-) or alpha- substituted aryl azo compounds,
and alpha- or beta-(HS-)azo or beta-thio, mercapto, or thiocarbonyl
alkyl compounds], or azo compounds.) Ligand can also contain
Poly[o-(HS-) or alpha- nonbinding N, O, S, or P atoms. or
beta-(HS-)azo compounds) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, or N--S Hexadentates) N--S Valence
R--N.dbd.N--C(.dbd.S)--N'R'R" Stabilizer #16: for
diazeneformothioamides, and Diazeneformothioamides,
R--N.dbd.N--CR'R"--C(.dbd.S)--NR"'R"" Diazeneacetothioamides, for
diazeneacetothioamides, where R, R', R", Bis(diazene- R"', and R""
represent H, NH.sub.2, or any formothioamides), organic functional
group wherein the number Bis(diazene- of carbon atoms ranges from 0
to 40, acetothioamides), optionally having halogen or polarizing or
Poly(diazene- water-insolubilizing/solubilizing groups
formothioamides), and attached. Ligand can also contain nonbinding
Poly(diazene- N, O, S, or P atoms. acetothioamides) (N--S
Bidentates, N--S Tetradentates, and N--S Hexadentates) N--S Valence
R--N.dbd.N--C(.dbd.S)--O--R' or Stabilizer #17:
R--N.dbd.N--CR'R"--C(.dbd.S)--O--R"' Diazenecarbothioic acids, for
diazenecarbothioic acids, and Diazenecarbodithioic acids,
R--N.dbd.N--C(.dbd.S)--S--R' or Bis(diazene-
R--N.dbd.N--CR'R"--C(.dbd.'S)--S--R"' carbothioic acids), for
diazenecarbodithoic acids, where R, R', Bis(diazene- R", and R"'
represent H, NH.sub.2, or any carbodithioic acids), organic
functional group wherein the number Poly(diazene- of carbon atoms
ranges from 0 to 40, carbothioic acids), optionally having halogen
or polarizing or Poly(diazene- water-insolubilizing/solubilizing
groups carbodithioic acids) and attached. Ligand can also contain
nonbinding derivatives thereof N, O, S, or P atoms. (N--S
Bidentates, N--S Tetradentates, N--S Hexadentates) N--S Valence
R--N.dbd.N--C(.dbd.S)--R'for Stabilizer #18:
diazeneformothioaldehydes, and Diazeneformo-
R--N.dbd.N--CR'R"--C(.dbd.S)--R"' for thioaldehydes,
diazeneacetothioaldehydes, where R, R', R", Diazeneaceto- and R"'
represent H, NH.sub.2, or any organic thioaldehydes, functional
group wherein the number of Bis(diazeneformo- carbon atoms ranges
from 0 to 40, optionally thioaldehydes), having halogen or
polarizing or water- Bis(diazeneaceto-
insolubilizing/solubilizing
groups attached. thioaldehydes), Ligand can also contain nonbinding
N, O, S, Poly(diazeneformo- or P atoms. thioaldehydes), and
Poly(diazeneaceto- thioaldehydes) (N--S Bidentates, N--S
Tetradentates and N--S Hexadentates) N--S Valence
RR'--N--C(.dbd.S)--N.dbd.N--C(.dbd.S)-- Stabilizer #19: NR"R'" or
RR'--N--C(.dbd.S)-- Diazenediformothioamides,
N.dbd.N--C(.dbd.O)--NR"R"' for Diazenediacetothioamides,
diazenediformothioamides, and RR'--N-- Bis(diazenedi-
C(.dbd.S)--CR"R"'--N.dbd.N--CR""R""'-- formothioamides),
C(.dbd.S)--NR"""R"""' or Bis(diazenedi-
RR'--N--C(.dbd.S)--CR"R'"--N.dbd.N-- acetothioamides),
CR""R""'--C(.dbd.O)--NR"""R"""' Poly(diazenedi- for
diazenediacetothioamides, where R, R', formothioamides), and R",
R"', R"", R""', R""", and R"""' represent Poly(diazenedi- H,
NH.sub.2, or any organic functional group acetothioamides) wherein
the number of carbon atoms ranges (N--S Tridentates from 0 to 40,
optionally having halogen or and N--S Hexadentates) polarizing or
water-insolubilizing/ solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence
R--O--C(.dbd.S)--N.dbd.N--C(.dbd.S)--O--R', Stabilizer #20:
R--O--C(.dbd.S)--CR'R"--N.dbd.N-- Diazenedicarbothioic acids,
CR'"R""--C(.dbd.S)--O--R""', Diazenedi- R--O--C(.dbd.S)--N.dbd.N---
C(.dbd.O)--O--R', carbodithioic acids, or
R--O--C(.dbd.S)--CR'R"--N- .dbd.'N-- Bis(diazenedi-
CR"'R""--C(.dbd.O)--O--R""' for carbothioic acids),
diazenedicarbothioic acids, and R--S-- Bis(diazenedi-
C(.dbd.S)--N.dbd.N--C(.dbd.S)--S--R' or carbodithioic acids),
R--S--C(.dbd.S)--CR'R"--N.dbd.N-- Poly(diazenedi-
CR"'R""--C(.dbd.S)--S--R""' for carbothioic acids),
diazenedicarbodithoic acids, where R, R', Poly(diazenedi- R", R"',
R"", and R"'" represent H, NH.sub.2, carbodithioic acids) and or
any organic functional group wherein the derivatives thereof number
of carbon atoms ranges from 0 to 40, (N--S Tridentates optionally
having halogen or polarizing or and N--S Hexadentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence
RC(.dbd.S)--N.dbd.N--C(.dbd.S)--R' or Stabilizer #21:
RC(.dbd.S)--N.dbd.N--C(.dbd.O)--R' for Diazenedi-
diazenediformothioaldehydes, and RC(.dbd.S)-- formothioaldehydes,
CR'R"--N.dbd.N--CR"'R""--C(.dbd.S)--R'"" or Diazenedi-
RC(.dbd.S)--CR'R"--N.dbd.N--CR"'R""-- acetothioaldehydes,
C(.dbd.O)--R""' for diazenediaceto- Bis(diazenedi- thioaldehydes,
where R, R', R", R"', R"", formothioaldehydes), and R""' represent
H, NH.sub.2, or any organic Bis(diazenedi- functional group wherein
the number of acetothioaldehydes), carbon atoms ranges from 0 to
40, optionally Poly(diazenedi- having halogen or polarizing or
water- formothioaldehydes), and insolubilizing/solubilizing groups
attached. Poly(diazenedi- Ligand can also contain nonbinding N, O,
S, acetothioaldehydes) or P atoms. (N--S Tridentates and N--S
Hexadentates) N--S Valence R--N.dbd.N--CR'.dbd.N--NR"R"', where R,
Stabilizer #22: R', R", and R"' represent H, or any organic
Ortho-thio (or -mercapto) functional group wherein the number of
Substituted Formazans, carbon atoms ranges from 0 to 40, optionally
Bis(o-thio or -mercapto having halogen or polarizing or water-
substituted formazans), insolubilizing/solubilizing groups and
Poly(o-thio or attached. (Must include ortho-thio or -mercapto
substituted mercapto substituted aryl R derivatives, formazans)
(N--S and beta-thio or mercapto substituted alkyl Bidentates, N--S
R derivatives.) Ligand can also contain Tridentates, N--S
nonbinding N, O, S, or P atoms. Tetradentates, and N--S
Hexadentates) N--S Valence RR'C.dbd.N--NC.dbd.R"R"' or Stabilizer
#23: RR'C.dbd.N--NR"R"' (for ketazines), Ortho-thio (or -mercapto)
where R, R', R", and R"' represent H, or any Substituted Azines
organic functional group wherein the number (including ketazines),
of carbon atoms ranges from 0 to 40, Bis(o-thio or mercapto
optionally having halogen or polarizing or substituted azines), and
water-insolubilizing/solubilizing groups Poly(o-thio or mercapto
attached. (Must include ortho-thio or substituted azines) mercapto
substituted aryl R derivatives, (N--S Bidentates, and beta-thio or
mercapto substituted alkyl N--S Tridentates, R derivatives.) Ligand
can also contain N--S Tetradentates, nonbinding N, O, S, or P
atoms. and N--S Hexadentates) N--S Valence RR'C.dbd.N--R", where R,
R', and R" Stabilizer #24: represent H, or any organic functional
group Schiff Bases with one wherein the number of carbon atoms
ranges Imine (C.dbd.N) Group and from 0 to 40, optionally having
halogen or with ortho- or alpha- or polarizing or
water-insolubilizing/ beta-thio or mercapto or solubilizing groups
attached. (Must contain thiocarbonyl substitution ortho- or alpha-
or beta- thio or mercapto (N--S Bidentates, or thiocarbonyl
substitution.) Ligand can also N--S Tridentates, contain nonbinding
N, O, S, or P atoms. N--S Tetradentates, N--S Pentadentates, or
N--S Hexadentates). Also includes Schiff Bases derived from the
reaction of carbonyl compounds with dithiocarbazates, and
hydrazones with ortho-S substitution. N--S Valence
RR'C.dbd.N--R"--N.dbd.CR"'R"" or Stabilizer #25:
R--N.dbd.C--R'--C.dbd.N--R' or Schiff Bases with two
RC.dbd.N--R'--N.dbd.CR", where R, R', R", Imine (C.dbd.N) Groups
R"', and R"" represent H, or any organic and with ortho- or alpha-
functional group wherein the number of or beta-thio or mercapto or
carbon atoms ranges from 0 to 40, optionally thiocarbonyl
substitution having halogen or polarizing or water- (N--S
Tridentates, insolubilizing/solubilizing groups attached. N--S
Tetradentates, (Must contain ortho- or alpha- or beta-thio or N--S
Pentadentates, mercapto or thiocarbonyl substitution.) or N--S
Hexadentates). Ligand can also contain nonbinding N, O, S, Also
includes Schiff Bases or P atoms. derived from the reaction of
carbonyl compounds with dithiocarbazates, and hydrazones with
ortho-S substitution. N--S Valence N(--R--N.dbd.CR'R").sub.3, where
R, R', and R" Stabilizer #26: represent H, or any organic
functional group Schiff Bases with three wherein the number of
carbon atoms ranges Imine (C.dbd.N) Groups and from 0 to 40,
optionally having halogen or with ortho- or alpha- or polarizing or
water-insolubilizing/ beta- thio or mercapto or solubilizing groups
attached. (Must contain thiocarbonyl substitution ortho- or alpha-
or beta-thio or mercapto or (N--S Tetradentates, thiocarbonyl
substitution.) Ligand can also N--S Pentadentates, contain
nonbinding N, O, S, or P atoms. or N--S Hexadentates). Also
includes Schiff Bases derived from the reaction of carbonyl
compounds with dithiocarbazates, and hydrazones with ortho-S
substitution. N--S Valence [R--CR'(--NR"R"')].sub.x--R""--[C(--
Stabilizer #27: SR""')R"""R"""'].sub.y , [R--CR'(--NR"R"')].sub.x--
Thioalkyl Amines R""--[C(--S--S--R""')R"""R"""'].sub.y, or
(Aminothiols or [R--CR'(--NR"R"')].sub.x--R""-- Aminodisulfides)
and LC(.dbd.S)R""'].sub.y for thioalkyl amines; and Thioalkyl
Imines [R--C(.dbd.NR')].sub.x--R"--[C(-- (Iminothiols or
SR"')R""R""'].sub.y, [R--C(.dbd.NR')].sub.x--R"-- Iminodisulfides)
[C(--S--[C(.dbd.S)R"'].sub.y for thioalkyl imines, (N--S
Bidentates, where R, R', H, NH.sub.2, or any organic N--S
Tridentates, functional group wherein the number of N--S
Tetradentates, and carbon atoms ranges from 0 to 40, optionally
N--S Hexadentates) having halogen or polarizing or water-
insolubilizing/solubilizing groups attached, and x and y = 1-6.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence [R(--NR'R")(--SR"')], Stabilizer #28:
[R(--NR'R")(--S--S--R"')], Thioaryl Amines and
[R(--NR'R")(--C(.dbd.S)R"'], Thioaryl Imines (N--S
[R(--NR'R").sub.x].sub.2S, Bidentates, N--S
[R(--NR'R").sub.x].sub.2-3R"'(--SR'"').sub.y , Tridentates, N--S
[R(--SR').sub.x].sub.2-3R"(--NR"'R"").sub.y, Tetradentates, and
[R(--NR'R").sub.x].sub.2S.sub.2, and N--S Hexadentates)
[R(--NR'R").sub.x].sub.2R"'(C(.dbd.S)).sub.yR"" for thioaryl
amines; and [R(--SR').sub.x]NH or [R(--SR').sub.x].sub.2NHNH for
thioaryl imines, where R, R', R", R"', and R"" represent H,
NH.sub.2, or any organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polanzing or water- insolubilizing/solubilizing groups attached,
and x = 0-2 and y = 1-4. Ligand can also contain nonbinding N, O,
S, or P atoms. N--S Valence Five membered heterocyclic ring(s)
Stabilizer #29: containing one, two, three, or four nitrogen
Five-Membered atoms. In addition, ligand contains additional
Heterocyclic Rings sulfur-containing substituents (usually thiols,
containing One, Two, mercaptans, disulfides, or thiocarbonyls) that
Three, or Four Nitrogen constitute S binding sites. Can include
other Atoms at least one ring systems bound to the heterocyclic
ring additional Sulfur Atom or to the S-containing substituent, but
they Binding Site not in a Ring do not coordinate with the
stabilized, high (N--S Bidentates, valence metal ion. Ring(s) can
also contain N--S Tridentates, O, S, or P atoms. This 5-membered
ring(s) N--S Tetradentates, and/or attached, uncoordinating rings
and/or or N--S Hexadentates) S-containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--S Valence Six
membered heterocyclic ring(s) Stabilizer #30: containing one, two,
three, or four nitrogen Six-Membered atoms. In addition, ligand
contains additional Heterocyclic Rings sulfur-containing
substituents (usually thiols, containing One, Two, mercaptans,
disulfides, or thiocarbonyls) that Three, or Four Nitrogen
constitute S binding sites. Can include other Atoms at least one
ring systems bound to the heterocyclic ring additional Sulfur Atom
or to the S-containing substituent, but they Binding Site not in a
Ring do not coordinate with the stabilized, high (N--S Bidentates,
valence metal ion. Ring(s) can also contain N--S Tridentates, O, S,
or P atoms. This 6-membered ring(s) N--S Tetradentates, and/or
attached, uncoordinating rings and/or or N--S Hexadentates)
S-containing substituent(s) may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--S Valence Five membered heterocyclic ring(s) Stabilizer #31:
containing one or two sulfur atoms. In Five-Membered addition,
ligand contains additional nitrogen- Heterocyclic Rings containing
substituents (usually amines, containing One or Two imines, or
hydrazides) that constitute N Sulfur Atoms at least one binding
sites. Can include other ring systems additional Nitrogen Atom
bound to the heterocyclic ring or to the Binding Site not in a Ring
N-containing substituent, but they do not (N--S Bidentates,
coordinate with the stabilized, high valence N--S Tridentates,
metal ion. Ring(s) can also contain O, S, N--S Tetradentates, or P
atoms. This 5-membered ring(s) and/or or N--S Hexadentates)
attached, uncoordinating rings and/or N-containingsubstituent(s)
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--S Valence Six
membered heterocyclic ring(s) Stabilizer #32: containing one or two
sulfur atoms. In Six-Membered addition, ligand contains additional
nitrogen- Heterocyclic Rings containing substituents (usually
amines, containing One or Two imines, or hydrazides) that
constitute N Sulfur Atoms at least one binding sites. Can include
other ring systems additional Nitrogen Atom bound to the
heterocyclic ring or to the Binding Site not in a Ring N-containing
substituent, but they do not (N--S Bidentates, coordinate with the
stabilized, high valence N--S Tridentates, metal ion. Ring(s) can
also contain O, S, or N--S Tetradentates, P atoms. This 6-membered
ring(s) and/or or N--S Hexadentates) attached, uncoordinating rings
and/or N-containingsubstituent(s) may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--S Valence Five membered heterocyclic ring(s) Stabilizer #33:
containing one, two, three, or four nitrogen Five-Membered atoms.
In addition, ligand contains additional Heterocyclic Rings
sulfur-containing rings that constitute S containing One, Two,
binding sites. Can include other ring systems Three, or Four
Nitrogen bound to the N- or S-containing heterocyclic Atoms at
least one rings, but they do not coordinate with the additional
Sulfur Atom stabilized, high valence metal ion. Ring(s) Binding
Site in a Separate can also contain O, S, or P atoms. This Ring
(N--S Bidentates, 5-membered ring(s) and/or additional N--S
Tridentates, S-containing ring(s) and/or attached, N--S
Tetradentates) uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--S Valence Six membered heterocyclic ring(s) Stabilizer #34:
containing one, two, three, or four nitrogen Six-Membered atoms. In
addition, ligand contains additional Heterocyclic Rings
sulfur-containing rings that constitute S containing One, Two,
binding sites. Can include other ring systems Three, or Four
Nitrogen bound to the N- or S- containing heterocyclic Atoms at
least one rings, but they do not coordinate with the additional
Sulfur Atom stabilized, high valence metal ion. Ring(s) Binding
Site in a Separate can also contain O, S, or P atoms. This Ring
(N--S Bidentates, 6-membered ring(s) and/or additional N--S
Tridentates, S-containing ring(s) and/or attached, N--S
Tetradentates) uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--S Valence Macrocyclic ligands containing two, three, Stabilizer
#35: four, six, eight, or ten binding sites Two-, Three-, Four-,
composed of nitrogen and sulfur to valence Six-, Eight-, and Ten-
stabilize the central metal ion. Can include Membered Macrocyclics,
other hydrocarbon or ring systems bound to Macrobicyclics, and this
macrocyclic ligand, but they do not Macropolycyclics coordinate
with the stabilized, high valence (including Catapinands, metal
ion. This ligand and/or attached, Cryptands, Cyclidenes, and
uncoordinating hydrocarbons/rings may or Sepulchrates) wherein all
may not have halogen or polarizing or water- Binding Sites are
composed insolubilizing/solubilizing groups attached. of Nitrogen
(usually amine or imine groups) or Sulfur (usually thiols,
mercaptans, or thiocarbonyls) and are not contained in Component
Heterocyclic Rings (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) N--S Valence Macrocyclic
ligands containing a total of Stabilizer #36: four, six, eight, or
ten heterocyclic rings Four-, Six-, Eight-, containing and nitrogen
or sulfur bindingc or Ten-Membered sites. Can include other
hydrocarbon/ring Macrocyclics, systems bound to this macrocyclic
ligand, Macrobicyclics, but they do not coordinate with the
Macropolycyclics stabilized, high valence metal ion. This
(including Catapinands, ligand and/or attached, uncoordinating
Cryptands, Cyclidenes, hydrocarbon/rings may or may not have and
Sepulchrates) halogen or polarizing or water-insolubilizing wherein
all Binding Sites groups attached. are composed of Nitrogen or
Sulfur and are contained in Component Heterocyclic Rings (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) N--S Valence
Macrocyclic ligands containing at least one Stabilizer #37:
heterocyclic ring. These heterocyclic rings Four-, Six-, Eight-,
provide nitrogen or sulfur binding sites to or Ten-Membered valence
stabilize the central metal ion. Other Macrocyclics, amine, imine,
thiol, mercapto, or Macrobicyclics, and thiocarbonyl binding sites
can also be Macropolycyclics included in the macrocyclic ligand, so
long (including Catapinands, as the total number of binding sites
is four, Cryptands, Cyclidenes, six, eight, or ten. Can include
other and Sepulchrates) hydrocarbon/ring systems bound to this
wherein all Binding Sites macrocyclic ligand, but they do not are
composed of Nitrogen coordinate with the stabilized, high valence
or Sulfur and are contained metal ion. This ligand and/or attached,
in a Combination of uncoordinating hydrocarbon/rings may or
Heterocyclic Rings and may not have halogen or polarizing or water-
Amine, Imine, Thiol, insolubilizing groups attached. Mercapto, or
Thiocarbonyl Groups (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, or N--S Hexadentates) N--O Valence
R'--N(--OH)--C(--R).dbd.N--R", where R, Stabilizer #1: R', and R"
represent H or any organic N--Hydroxy(or N,N'- functional group
wherein the number of dihydroxy)amidines and carbon atoms ranges
from 0 to 40, optionally N--Hydroxy(or N,N'- having halogen or
polarizing or water-insol dihydroxy)diamidines
ubilizing/solubilizing groups attached. (N--O Bidentates, Ligand
can also contain nonbinding N, O, S, N--O Tridentates, or P atoms.
or N--O Tetradentates) N--O Valence
RR'--N--C(.dbd.NH)--NR"--CO--NR"'R"" Stabilizer #2: for
guanylureas, and RR'--N--C(.dbd.NH)-- Guanylureas,
NR"--NH--CO--NR"'R"" for Guanidinoureas, guanidinoureas, where R,
R', R", R"', and Bis(guanylureas), R"" represent H, NH.sub.2, or
any organic Bis(guanidinoureas), functional group wherein the
number of Poly(guanylureas), and carbon atoms ranges from 0 to 40,
optionally Poly(guanidinoureas) having halogen or polarizing or
water- (N--O Bidentates and insolubilizing/solubilizing groups
attached. N--O Tetradentates) Ligand can also contain nonbinding N,
O, S, or P atoms. N--O Valence RR'--N--C(.dbd.NH)--NR"-- -CO--R"'
for Stabilizer #3: N-amidinoamides, or RR'--N--C(.dbd.NH)--
Amidinoamides, CR"R"'--CO--N--R""R""' Guanidinoamides, for
2-amidinoacetamides, and Bis(amidinoamides),
RR'--N--C(.dbd.NH)--NR"--NH--CO--R"' Bis(guanidinoamides), for
guanidinoamides, where R, R', R", R"', Poly(amidinoamides), and
R"", and R""' represent H, NH.sub.2, or Poly(guanidinoamides) any
organic functional group wherein the (including both N- number of
carbon atoms ranges from 0 to 40, amidinoamides and optionally
having halogen or polarizing or 2-amidinoacetamides)
water-insolubilizing/solubilizing groups (N--O Bidentates attached.
Ligand can also contain nonbinding and N--O Tetradentates) N, O, S,
or P atoms. N--O Valence R--C(.dbd.NH)--NR'--CO--R", where R,
Stabilizer #4: R', and R", and R'" represent H or any
Imidoylamides, organic functional group wherein the number
Bis(imidoylamides), of carbon atoms ranges from 0 to 40,
Poly(imidoylamides) optionally having halogen or polarizing or
(N--O Bidentates and water-insolubilizing/solubilizi- ng groups
N--O Tetradentates) attached. Ligand can also contain nonbinding N,
O, S, or P atoms. N--O Valence RR'--N--C(.dbd.NH)--O--CO--NR"R"',
Stabilizer #5: where R, R', R", and R"' represent H, NH.sub.2,
O-Amidinocarbamates, or any organic functional group wherein the
Bis(O-amidinocarbamates), number of carbon atoms ranges from 0 to
40, and Poly(O- optionally having halogen or polarizing or
amidinocarbamates) water-insolubilizing/solubilizing groups (N--O
Bidentates and attached. Ligand can also contain nonbinding N--O
Tetradentates) N, O, S, or P atoms. N--O Valence
RR'--N--C(.dbd.NH)--S--CO--NR"R"- ', Stabilizer #6: where R, R',
R", and R"' represent H, NH.sub.2, 5-Amidinothiocarbamates, or any
organic functional group wherein the Bis(S-amidinothio- number of
carbon atoms ranges from 0 to 40, carbamates), and Poly(S-
optionally having halogen or polarizing or amidinothiocarbamates)
water-insolubilizing/solubilizing groups (N--O Bidentates and
attached. Ligand can also contain nonbinding N--O Tetradentates) N,
O, S, or P atoms. N--O Valence (NH.dbd.)(NH.dbd.)P(OR)(OR'), where
R, R', and Stabilizer #7: R" represent H, NH.sub.2, or any organic
Diimidosulfuric Acid, functional group wherein the number of
Bis(diimidosulfuric carbon atoms ranges from 0 to 40, optionally
acid), and derivatives having halogen or polarizing or water-
thereof (N--O insolubilizing/solubilizing groups attached.
Bidentates and N--O Ligand can also contain nonbinding N, O, S,
Tetradentates) or P atoms. N--O Valence
(NH.dbd.)P(--OR)(--OR')(--OR"), where R, Stabilizer #8: R', and R"
represent H, NH.sub.2, or any organic Phosphorimidic Acid,
functional group wherein the number of Bis(phosphorimidic acid);
carbon atoms ranges from 0 to 40, optionally and
Poly(phosphorimidic having halogen or polarizing or water- acid),
and derivatives insolubilizing/solubilizing groups attached.
thereof (N--O Bidentates) Ligand can also contain nonbinding N, O,
S, or P atoms. N--O Valence (O.dbd.)P(--NRR')(--NR"R"')(--NR""R"-
"'), Stabilizer #9: where R, R', R", R"', R"", and R""' represent
H, Phosphoric Triamides, NH.sub.2, or any organic functional group
Bis(phosphoric triamides), wherein the number of carbon atoms
ranges and Poly(phosphoric from 0 to 40, optionally having halogen
or triamides) (N--O polarizing or water-insolubilizing/ Bidentates
and solubilizing groups attached. Ligand can also N--O
Tetradentates) contain nonbinding N, O, S, or P atoms. N--O Valence
(O.dbd.)P(--NRR')(--OR")(--OR"') Stabilizer #10: for phosphoramidic
acid and (O.dbd.)P(-- Phosphoramidic Acid, NRR')(--NR"R"')(--OR"")
for Phosphorodiamidic Acid, phosphorodiamidic acid, where R, R',
R", Bis(phosphoramidic acid), R"', and R""represent H, NH.sub.2, or
any Bis(phosphorodiamidic organic functional group wherein the
number acid), Poly(phosphor- of carbon atoms ranges from 0 to 40,
amidic acid), Poly(phosp- optionally having halogen or polarizing
or horodiamidic acid), and water-insolubilizing/solubilizing groups
derivatives thereof attached. Ligand can also contain nonbinding
(N--O Bidentates N, O, S, or P atoms. and N--O Tetradentates) N--O
Valence R'--C(.dbd.O)--N.dbd.C(--R)(--NHR"), where Stabilizer #11:
R is an aromatic derivative (i.e. --C.sub.6H.sub.5), N-Acyl
7-Aminobenzyl- and R'and R" represent H, NH.sub.2, or any
idenimines (N--O organic functional group wherein the number
Bidentates or of carbon atoms ranges from 0 to 40, N--O
Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence
R--C(.dbd.NOH)--R' for oximes, and Stabilizer #12:
R--C(.dbd.NOH)--C(.dbd.NOH)--R' for Oximes, Dioximes, dioximes,
where R and R' represent H, NH.sub.2, and Poly(oximes) or any
organic functional group wherein the (N--O Bidentates, number of
carbon atoms ranges from 0 to 40, N--O Tridentates, optionally
having halogen or polarizing or and N--O Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence
R--C(.dbd.O)--C(.dbd.NOH)--R', where R and Stabilizer #13: R'
represent H, NH.sub.2, or any organic Carbonyl oximes, functional
group wherein the number of Bis(carbonyl oximes), carbon atoms
ranges from 0 to 40, optionally and Poly(carbonyl oximes) having
halogen or polarizing or water- (N--O Bidentates,
insolubilizing/solubilizing groups attached. N--O Tridentates,
Ligand can also contain nonbinding N, O, S, and N--O Tetradentates)
or P atoms. N--O Valence R--C(.dbd.N--R")--C(.dbd.N- OH)--R', where
Stabilizer #14: R, R', and R" represent H, NH.sub.2, or any Imine
oximes, organic functional group wherein the Bis(imine oximes), and
number of carbon atoms ranges from 0 to 40, Poly(imine oximes)
optionally having halogen or polarizing or (including 2-nitrogen
water-insolubilizing/solubilizing groups heterocyclic oximes)
attached. Ligand can also contain nonbinding (N--O Bidentates, N,
O, S, or P atoms. N--O Tridentates, N--O Tetradentates, and N--O
Hexadentates) N--O Valence R--CH(--OH)--C(.dbd.NOH)--R', where R,
Stabilizer #15: R', and R" represent H, NH.sub.2, or any Hydroxy
oximes, organic functional group wherein the number Bis(hydroxy
oximes), and of carbon atoms ranges from 0 to 40, Poly(hydroxy
oximes) optionally having halogen or polarizing or (including
2-oxygen water-insolubilizing/solubilizing groups heterocyclic
oximes) attached. Ligand can also contain nonbinding (N--O
Bidentates, N, O, S, or P atoms. N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) N--O Valence
RR'--C(--NH--R")--C(.dbd.NO- H)--R'" Stabilizer #16: where R, R',
R", and R"'represent H, NH.sub.2, Amino oximes, or any organic
functional group wherein the Bis(amino oximes), and number of
carbon atoms ranges from 0 to 40, Poly(amino oximes) optionally
having halogen or polarizing or (N--O Bidentates,
water-insolubilizing/solubilizing groups N--O Tridentates,
attached. Ligand can also contain nonbinding N--O Tetradentates, N,
O, S, or P atoms. and N--O Hexadentates) N--O Valence
RR'--N--C(.dbd.NOH)--R", where R, R', Stabilizer #17: and R"
represent H, NH.sub.2, or any organic Amido oximes, functional
group wherein the number of Bis(amido oximes), and carbon atoms
ranges from 0 to 40, optionally Poly(amido oximes) having halogen
or polarizing or water- (N--O Bidentates,
insolubilizing/solubilizing groups attached. N--O Tridentates,
Ligand can also contain nonbinding N, O, S, N--O Tetradentates, or
P atoms. and N--O Hexadentates) N--O Valence
R--N.dbd.N--C(.dbd.NOH)--R' or RR'C-- Stabilizer #18:
.dbd.N--NR"--C(.dbd.NOH)--R"', where R, Azo oximes, R', R", and
R"'represent H, NH.sub.2, or any Bis(azo oximes), organic
functional group wherein the and Poly(azo oximes) number of carbon
atoms ranges from 0 to 40, (N--O Bidentates, optionally having
halogen or polarizing or N--O Tridentates, water-insolubilizing/so-
lubilizing groups N--O Tetradentates, attached. (R is typically an
aryl group.) and N--O Hexadentates). Ligand can also contain
nonbinding N, O, S, Also includes or P atoms. hydrazone oximes.
N--O Valence o-(ON--)(HO-)Ar, where Ar represents an Stabilizer
#19: aromatic group or heterocyclic wherein the 2--Nitrosophenols
number of carbon atoms ranges from 6 to 40, (o-Quinone monoximes)
optionally having halogen or polarizing or (N--O Bidentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence
o-(O.sub.2N--)(HO-)Ar, where Ar represents an Stabilizer #20:
aromatic group or heterocyclic wherein the 2--Nitrophenols number
of carbon atoms ranges from 6 to 40, (N--O Bidentates) optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence R--C(.dbd.O)--NR'--OH or Stabilizer #21:
R--C(--OH).dbd.N--OH, where R and R' Hydroxamates represent H,
NH.sub.2, or any organic functional (Hydroxylamines), group wherein
the number of carbon atoms Bis(hydroxamates), and ranges from 0 to
40, optionally having Poly(hydroxamates) halogen or polarizing or
water- (N--O Bidentates, insolubilizing/solubilizing groups N--O
Tetradentates, attached. Ligand can also contain nonbinding and
N--O Hexadentates) N, O, S, or P atoms. N--O Valence
R--N(--NO)--OH, where R represents Stabilizer #22: any organic
functional group wherein the N-Nitrosohydroxylamines, number of
carbon atoms ranges from 1 to 40, Bis(N-nitrosohydroxyl- optionally
having halogen or polarizing or amines), and Poly(N- water
insolubilizing/solubilizing groups nitrosohydroxylamines) attached.
(R is typically an aryl or (N--O Bidentates, heterocyclic group.)
Ligand can also contain N--O Tetradentates, nonbinding N, O, S. or
P atoms. and N--O Hexadentates) N--O Valence
R--CH(--NHR')--C(.dbd.O)(--OH) for Stabilizer #23: amino acids and
ortho-aminocarboxylic Amino Acids and acids, and
R--CH(--NHR')--C(.dbd.O)-- ortho-Aminocarboxylic
(NR"--)CH(--R"')--C(.dbd.O)(--OH) Acids, Peptides, for peptides,
where R, R', R", and R"' Polypeptides, and Proteins represent any
organic functional group [N--O Bidentates, wherein the number of
carbon atoms ranges N--O Tridentates, and from 1 to 40, optionally
having halogen or N--O Tetradentates; polarizing or
water-insolubilizing/ possibly S--O dentates solubilizing groups
attached. Ligand can also for sulfur-contg. examples contain
nonbinding N, O, S, or P atoms. such as penicillamine and cystine]
N--O Valence RCONR'R", where R, R', and R" represent Stabilizer
#24: H, NH.sub.2, or any organic functional group Amides,
Bis(amides), wherein N--O the number of carbon atoms and
Poly(amides), ranges from 0 to 40, optionally having including
lactams halogen or polarizing or water- (N--O Bidentates,
insolubilizing/solubilizing groups Tridentates, and attached.
Ligand can also contain nonbinding N--O Tetradentates) N, O, S, or
P atoms. N--O Valence RR'--N--C(.dbd.O)--NR"--N.dbd.CR"'R"",
Stabilizer #25: where R, R', R", R"', and R"" represent H,
Semicarbazones, or any organic functional group wherein the
Bis(semicarbazones), and number of carbon atoms ranges from 0 to
40, Poly(semicarbazones) optionally having halogen or polarizing or
(N--O Bidentates, water-insolubilizing/solubilizing groups N--O
Tetradentates, and attached. Ligand can also contain nonbinding
N--O Hexadentates) N, O, S, or P atoms. N--O Valence
R--C(.dbd.O)--NR'--N.dbd.CR"R"', where Stabilizer #26: R, R', R",
and R"' represent H, or any Acyl hydrazones, organic functional
group wherein the number Bis(acyl hydrazones), and of carbon atoms
ranges from 0 to 40, Poly(acyl hydrazones) optionally having
halogen or polarizing or (N--O Bidentates, water-insolubilizing/so-
lubilizing groups N--O Tetradentates, attached. Ligand can also
contain nonbinding and N--O Hexadentates) N, O, S, or P atoms. N--O
Valence R--N.dbd.N--C(.dbd.O)--NR'--N--R"R"', Stabilizer #27: where
R, R', R", and R"' represent H, or any Carbazones organic
functional group wherein the number (Diazenecarboxylic of carbon
atoms ranges from 0 to 40, hydrazides), optionally having halogen
or polarizing or Bis(carbazones), and
water-insolubilizing/solubilizing groups Poly(carbazones) attached.
Ligand can also contain nonbinding (N--O Bidentates, N, O, S, or P
atoms. N--O Tetradentates, and N--O Hexadentates) N--O Valence
R--N.dbd.N--R' for azo compounds, Stabilizer #28:
R--N.dbd.N--NH--R' for triazenes, where R, Azo compounds including
and R' represent H or any organic functional triazenes with
hydroxyl group wherein the number of carbon atoms or carboxy or
carbonyl ranges from 0 to 40, optionally having substitution at the
ortho- halogen or polarizing or water- (for aryl) or alpha- or
beta- insolubilizing/solubilizing groups (for alkyl) positions,
attached. (Must include ortho-hydroxy or Bis[o-(HO--) or alpha-
carboxy or carbonyl substituted aryl azo or beta-(HO--)azo
compounds, and alpha- or beta-hydroxy or compounds], or carboxy or
carbonyl alkyl azo compounds.) Poly[o-(HO--) or alpha- Ligand can
also contain nonbinding N, O, S, or beta-(HO--)azo or P atoms.
compounds) (N--O Bidentates, N--O Tridentates, N--O Tetradentates,
or N--O Hexadentates) N--O Valence R--N.dbd.N--C(.dbd.O)--NR'R"
Stabilizer #29: for diazeneformamides, and Diazeneformamides,
R--N.dbd.N--CR'R"--C(.dbd.O)--NR'"R "" Diazeneacetamides, for
diazeneacetamides, where R, R', R", R"', Bis(diazeneformamides),
and R"" represent H, NH.sub.2, or any organic
Bis(diazeneacetamides), functional group wherein the number of
Poly(diazeneformamides), carbon atoms ranges from 0 to 40,
optionally and Poly(diazene- having halogen or polarizing or water-
acetamides) insolubilizing/solubilizing groups attached. (N--O
Bidentates, Ligand can also contain nonbinding N, O, S, N--O
Tetradentates, or P atoms. and N--O Hexadentates) N--O Valence
R--N.dbd.N--C(.dbd.O)--O--R' Stabilizer #30: for diazeneformic
acid, and Diazeneformic acids, R--N.dbd.N--CR'R"--C(.dbd.O)--O--R"'
Diazeneacetic acids, for diazeneacetic acid, where R, R', R", and
Bis(diazeneformic acids), R"' represent H, NH.sub.2, or any organic
Bis(diazeneacetic acids), functional group wherein the number of
Poly(diazeneformic acids), carbon atoms ranges from 0 to 40,
optionally Poly(diazeneacetic acids), having halogen or polarizing
or water- and derivatives thereof insolubilizing/solubilizing
groups attached. (N--O Bidentates, Ligand can also contain
nonbinding N, O, S, N--O Tetradentates, or P atoms. N--O
Hexadentates) N--O Valence R--N.dbd.N--C(.dbd.O)--R' Stabilizer
#31: for diazeneformaldehydes, and Diazeneformaldehydes,
R--N.dbd.N--CR'R"--C(.dbd.O)--R"' for Diazeneacetaldehydes,
diazeneacetaldehydes, where R, R', R", and Bis(diazene- R"'
represent H, NH.sub.2, or any organic formaldehydes), functional
group wherein the number of Bis(diazene- carbon atoms ranges from 0
to 40, optionally acetaldehydes), having halogen or polarizing or
water- Poly(diazene- insolubilizing/solubilizing groups attached.
formaldehydes), and Ligand can also contain nonbinding N, O, S,
Poly(diazene- or P atoms. acetaldehydes) (N--O Bidentates, N--O
Tetradentates and N--O Hexadentates) N--O Valence
RR'--N--C(.dbd.O)--NN--C(.dbd.O)--NR"R"' Stabilizer #32: for
diazenediformamides, and RR'--N-- Diazenediformamides,
C(.dbd.O)--CR"R"'--N.dbd.N--CR""R""'-- Diazenediacetamides,
C(.dbd.O)--NR"""R"""'for diazenedi- Bis(diazenedi- acetamides,
where R, R', R", R"', R"", R""', formamides), R""", and R"""'
represent H, NH.sub.2, or any Bis(diazene- organic functional group
wherein the diacetamides), number of carbon atoms ranges from
Poly(diazenedi- 0 to 40, optionally having halogen or formamides),
and polarizing or water-insolubilizing/ Poly(diazenedi-
solubilizing groups attached. Ligand can also acetamides) contain
nonbinding N, O, S, or P atoms. (N--O Tridentates and N--O
Hexadentates) N--O Valence
R--O--C(.dbd.O)--N.dbd.N--C(.dbd.O)--O--R' Stabilizer #33: for
diazenediforrnic acid, and Diazenediformic acids,
R--O--C(.dbd.O)--CR'R"N.dbd.N--CR"'R""-- Diazenediacetic acids,
C(.dbd.O)--R'"" for diazenediacetic acid, Bis(diazenediformic
acids), where R, R', R", R"', R"", and R""' represent
Bis(diazenediacetic acids), H, NH.sub.2, or any organic functional
group Poly(diazenediformic wherein the number of carbon atoms
ranges acids), Poly(diazene- from 0 to 40, optionally having
halogen or diacetic acids) and polarizing or water-insolubilizing/
derivatives thereof solubilizing groups attached. (N--O Tridentates
Ligand can also contain nonbinding and N--O Hexadentates) N, O, S,
or P atoms. N--O Valence RC(.dbd.O)--N.dbd.N--C(.dbd.O)--R'
Stabilizer #34: for diazenediformaldehydes, and
Diazenediformaldehydes, RC(.dbd.O)--CR 'R"--N.dbd.N--CR"'R""--
Diazenediacetaldehydes, C(.dbd.O)--R""' for diazenediacetaldehydes,
Bis(diazenedi- where R, R', R", R"', R"", and R""' represent
formaldehydes), H, NH.sub.2, or any organic functional group
Bis(diazenedi- wherein the number of carbon atoms ranges
acetaldehydes), from 0 to 40, optionally having halogen or
Poly(diazenedi- polarizing or water-insolubilizing/ formaldehydes),
and solubilizing groups attached. Ligand can Poly(diazenedi- also
contain nonbinding N, O, S, or acetaldehydes) P atoms. (N--O
Tridentates and N--O Hexadentates) N--O Valence
R--N.dbd.N--CR'.dbd.N--NR"R"', where Stabilizer #35: R, R', R", and
R"' represent H, or any Ortho-hydroxy (or organic functional group
wherein the number -carboxy) Substituted of carbon atoms ranges
from 0 to 40, Formazans, Bis(o-hydroxy optionally having halogen or
polarizing or or -carboxy substituted
water-insolubilizing/solubilizing groups formazans), and attached.
(Must include ortho-hydroxy or Poly(o-hydroxy or -carboxy carboxy
substituted aryl R derivatives, and substituted formazans)
beta-hydroxy or carboxy substituted alkyl R (N--O Bidentates,
derivatives.) Ligand can also contain N--O Tridentates, nonbinding
N, O, S, or P atoms. N--O Tetradentates, and N--O Hexadentates)
N--O Valence RR'C.dbd.N--N.dbd.CR"R"'o- r Stabilizer #36:
RR'C.dbd.N--NR"R"'(for ketazines), where Ortho-hydroxy (or R, R',
R", and R"' represent H, or any -carboxy) Substituted organic
functional group wherein the number Azines (including of carbon
atoms ranges from 0 to 40, ketazines), Bis(o- optionally having
halogen or polarizing or hydroxy or carboxy
water-insolubilizing/solubilizing groups substituted azines), and
attached. (Must include ortho-hydroxy or Poly(o-hydroxy or carboxy
substituted aryl R derivatives, carboxy substituted azines) and
beta- hydroxy or carboxy substituted (N --O Bidentates, alkyl R
derivatives.) Ligand can also contain N--O Tridentates, nonbinding
N, O, S, or P atoms. N--O Tetradentates, and N--O Hexadentates)
N--O Valence RR'C.dbd.N--R", where R, R', and R" Stabilizer #37:
represent H, or any organic functional group Schiff Bases with
wherein the number of carbon atoms ranges one Imine (C.dbd.N) Group
from 0 to 40, optionally having halogen or and with ortho- or
alpha- polarizing or water-insolubilizing/ or beta-hydroxy or
carboxy solubilizing groups attached. (Must contain or carbonyl
substitution ortho- or alpha- or beta- hydroxy or carboxy (N--O
Bidentates, or carbonyl substitution.) Ligand can also N--O
Tridentates, contain nonbinding N, O, S, or P atoms. N--O
Tetradentates, N--O Pentadentates, or N--O Hexadentates). Also
includes hydrazones with ortho-O substitution. N--O Valence
RR'C.dbd.N--R"--N.dbd.CR"'R"" or Stabilizer #38:
R--N.dbd.C--R'--C.dbd.N--R' or Schiff Bases with
RC.dbd.N--R'--N.dbd.CR", where R, R', R", two Imine (C.dbd.N)
Groups R"', and R"" represent H, or any organic and with ortho- or
alpha- functional group wherein the number of or beta-hydroxy or
carboxy carbon atoms ranges from 0 to 40, optionally or carbonyl
substitution having halogenor polarizing or water- (N--O
Tridentates, insolubilizing/solubilizing groups attached. N--O
Tetradentates, (Must contain ortho- or alpha- or beta- N--O
Pentadentates, or hydroxy or carboxy or carbonyl substitution.)
N--O Hexadentates). Ligand can also contain nonbinding N, O, S,
Also includes hydrazones or P atoms. with ortho-O substitution.
N--O Valence N(--R--N.dbd.CR'R").sub.3, where R, R', and R"
Stabilizer #39: represent H, or any organic functional group Schiff
Bases with wherein the number of carbon atoms ranges three Imine
(C.dbd.N) from 0 to 40, optionally having halogen or Groups and
with ortho- polarizing or water-insolubilizing/ or alpha- or beta-
solubilizing groups attached. (Must contain hydroxy or carboxy or
ortho- or alpha- or beta-hydroxy or carboxy carbonyl substitution
or carbonyl substitution.) Ligand can also (N--O Tetradentates,
contain nonbinding N, O, S, or P atoms. N--O Pentadentates, or N--O
Hexadentates). Also includes hydrazones with ortho-O substitution.
N--O Valence
[R--C(NR'R")].sub.x--R"--[Si(--OR"').sub.zR"".sub.3-z].sub.y
Stabilizer #40: where R, R', R", R"', and R"" represent H,
Silylaminoalcohols NH.sub.2, or any organic functional group (N--O
Bidentates, wherein the number of carbon atoms ranges N--O
Tridentates, from 0 to 40, optionally having halogen or N--O
Tetradentates, polarizing or water-insolubilizing/ and N--O
Hexadentates) solubilizing groups attached, and x and y = 1-6, z
=1-3. Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence [R--C(.dbd.NR')].sub.x--R"--[C(--OR"')R""R""'].sub.y
Stabilizer #41: or
[R--C(.dbd.NR')].sub.x--R"--[C(.dbd.O)R"'].sub.y, Hydroxyalkyl
Imines where R, R', R", R"', R"", and R""' represent (Imino
Alcohols) H, NH.sub.2, or any organic functional group (N--O
Bidentates, wherein the number of carbon atoms ranges N--O
Tridentates, from 0 to 40, optionally having halogen N--O
Tetradentates, or polarizing or water-insolubilizing/ and N--O
Hexadentates) solubilizing groups attached, and x and y = 1-6.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence [R(--NR'R")(--OR"')], Stabilizer #42:
[R(--NR'R")(--C(.dbd.O)R"'], Hydroxyaryl Amines
[R(--NR'R").sub.x].sub.2O, and Hydroxyaryl Imines
[R(--NR'R").sub.x].sub.2-3R"'(--OR'"').sub.y, (N--O Bidentates,
[R(--OR').sub.x].sub.2-3R"(--NR"'R"").sub.y, and N--O Tridentates,
[R(--NR'R").sub.x].sub.2R""(C(.dbd.O)).sub.yR"" for N--O
Tetradentates, hydroxyaryl amines; and [R(--OR').sub.x].sub.2NH or
and N--O Hexadentates) [R(--OR').sub.x].sub.2NHNH for hydroxyaryl
imines, where R, R', R", R"', and R"" represent H, NH.sub.2, or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/ solubilizing groups attached, and x = O-2 and
y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Five membered heterocyclic ring(s) Stabilizer #43:
containing one, two, three, or four nitrogen Five-Membered atoms.
In addition, ligand contains additional Heterocyclic Rings
oxygen-containing substituents (usually containing One, Two,
hydroxy, carboxy or carbonyl groups) that Three, or Four Nitrogen
constitute O binding sites. Can include other Atoms at least one
ring systems bound to the heterocyclic ring additional Oxygen Atom
or to the O-containing substituent, but they Binding Site not in a
Ring do not coordinate with the stabilized, high (N--O Bidentates,
valence metal ion. Ring(s) can also contain N--O Tridentates, O, S,
or P atoms. This 5-membered ring(s) N--O Tetradentates, and/or
attached, uncoordinating rings and/or or N--O Hexadentates)
O-containing substituent(s) may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--O Valence Six membered heterocyclic ring(s) Stabilizer #44:
containing one, two, three, or four nitrogen Six-Membered atoms. In
addition, ligand contains additional Heterocyclic Rings
oxygen-containing substituents (usually containing One, Two,
hydroxy, carboxy, or carbonyl groups) that Three, or Four Nitrogen
constitute O binding sites. Can include other Atoms at least one
ring systems bound to the heterocyclic ring additional Oxygen Atom
or to the O-containing substituent, but they Binding Site not in a
Ring do not coordinate with the stabilized, high (N--O Bidentates,
valence metal ion. Ring(s) can also contain N--O Tridentates, O, S,
or P atoms. This 6-membered ring(s) N--O Tetradentates, and/or
attached, uncoordinating rings and/or or N--O Hexadentates)
O-containing substituent(s) may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--O Valence Five membered heterocyclic ring(s) Stabilizer #45:
containing one or two oxygen atoms. In Five-Membered addition,
ligand contains additional nitrogen- Heterocyclic Rings containing
substituents (usually amines, containing One or imines, or
hydrazides) that constitute N Two Oxygen Atoms at binding sites.
Can include other ring systems least one additional bound to the
heterocyclic ring or to the Nitrogen Atom Binding N-containing
substituent, but they do not Site not in a Ring coordinate with the
stabilized, high valence (N--O Bidentates, metal ion. Ring(s) can
also contain O, S, N--O Tridentates, or P atoms. This 5-membered
ring(s) and/or N--O Tetradentates, attached, uncoordinating rings
and/or or N--O Hexadentates) N-containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--O Valence Six
membered heterocyclic ring(s) Stabilizer #46: containing one or two
oxygen atoms. In Six-Membered addition, ligand contains additional
nitrogen- Heterocyclic Rings containing substituents (usually
amines, containing One or imines, or hydrazides) that constitute N
Two Oxygen Atoms at binding sites. Can include other ring systems
least one additional bound to the heterocyclic ring or to the
Nitrogen Atom Binding N-containing substituent, but they do not
Site not in a Ring coordinate with the stabilized, high valence
(N--O Bidentates, metal ion. Ring(s) can also contain O, S, or N--O
Tridentates, P atoms. This 6-membered ring(s) and/or N--O
Tetradentates, attached, uncoordinating rings and/or or N--O
Hexadentates) N-containingsubstituent(s) may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. N--O Valence Five membered heterocyclic ring(s)
Stabilizer #47: containing one, two, three, or four nitrogen
Five-Membered atoms. In addition, ligand contains additional
Heterocyclic Rings oxygen-containing rings that constitute O
containing One, Two, binding sites. Can include other ring systems
Three, or Four bound to the N- or O-containing heterocyclic
Nitrogen Atoms at rings, but they do not coordinate with the least
one additional stabilized, high valence metal ion. Ring(s) Oxygen
Atom Binding can also contain O, S, or P atoms. This Site in a
Separate Ring 5-membered ring(s) and/or additional O-- (N--O
Bidentates, containing ring(s) and/or attached, N--O Tridentates,
uncoordinating rings may or may not have N--O Tetradentates)
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. N--O Valence Six membered heterocyclic ring(s) Stabilizer
#48: containing one, two, three, or four nitrogen Six-Membered
atoms. In addition, ligand contains additional Heterocyclic Rings
oxygen-containing rings that constitute O containing One, binding
sites. Can include other ring systems Two, Three, or Four bound to
the N- or O- containing heterocyclic Nitrogen Atoms at rings, but
they do not coordinate with the least one additional stabilized,
high valence metal ion. Ring(s) Oxygen Atom Binding can also
contain O, S, or P atoms. This Site in a Separate Ring 6-membered
ring(s) and/or additional (N--O Bidentates, O-containing ring(s)
and/or attached, N--O Tridentates, uncoordinating rings may or may
not have N--O Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--O Valence
Macrocyclic ligands containing two, three, Stabilizer #49: four,
six, eight, or ten binding sites Two-, Three-, Four-, composed of
nitrogen and oxygen to valence Six-, Eight-, and Ten- stabilize the
central metal ion. Can include Membered Macrocyclics, other
hydrocarbon or ring systems bound to Macrobicyclics, this
macrocyclic ligand, but they do not and Macropolycyclics coordinate
with the stabilized, high valence (including Catapinands, metal
ion. This ligand and/or attached, Cryptands, Cyclidenes, and
uncoordinating hydrocarbons/rings may or Sepulchrates) wherein all
may not have halogen or polarizing or water- Binding Sites are
insolubilizing/solubilizing groups attached. composed of Nitrogen
(usually amine or imine groups) or Oxygen (usually hydroxy,
carboxy, or carbonyl groupss) and
are not contained in Component Heterocyclic Rings (N--O Bidentates,
N--O Tridentates, N--O Tetradentates, and N--O Hexadentates) N--O
Valence Macrocyclic ligands containing a total of Stabilizer #50:
four, six, eight, or ten heterocyclic rings Four-, Six-, Eight-,
containing nitrogen or oxygen binding sites. or Ten-Membered Can
include other hydrocarbon/ring systems Macrocyclics, bound to this
macrocyclic ligand, but they Macrobicyclics, and do not coordinate
with the stabilized, high Macropolycyclics valence metal ion. This
ligand and/or (including Catapinands, attached, uncoordinating
hydrocarbon/rings Cryptands, Cyclidenes, may or may not have
halogen or polarizing and Sepulchrates) or water-insolubilizing
groups attached. wherein all Binding Sites are composed of Nitrogen
or Oxygen and are contained in Component Heterocyclic Rings (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) N--O Valence Macrocyclic ligands containing at least
one Stabilizer #51: heterocyclic ring. These heterocyclic rings
Four-, Six-, Eight-, provide nitrogen or oxygen binding sites to or
Ten-Membered valence stabilize the central metal ion. Other
Macrocyclics, amine, imine, hydroxy, carboxy, or carbonyl
Macrobicyclics, and binding sites can also be included in the
Macropolycyclics macrocyclic ligand, so long as the total
(including Catapinands, number of binding sites is four, six,
eight, Cryptands, Cyclidenes, or ten. Can include other
hydrocarbon/ring and Sepulchrates) systems bound to this
macrocyclic ligand, wherein all Binding but they do not coordinate
with the Sites are composed of stabilized, high valence metal ion.
Nitrogen or Oxygen and This ligand and/or attached, are contained
in a uncoordinating hydrocarbon/rings may or Combination of may not
have halogen or polarizing or Heterocyclic Rings and
water-insolubilizing groups attached. Amine, Imine, Hydroxy,
Carboxy, or Carbonyl Groups (N--O Bidentates, N--O Tridentates,
N--O Tetradentates, or N--O Hexadentates) S--O Valence
R--C(.dbd.S)--CR'R"--C(.dbd.O)--R"' where Stabilizer #1: R, R', R",
and R"' represent H, NH.sub.2, or any 1,3-Monothioketones organic
functional group wherein the number (Monothio-beta- of carbon atoms
ranges from 0 to 40, ketonates), optionally having halogen or
polarizing or 1,3,5-Monothioketones,
water-insolubilizing/solubilizing groups 1,3,5-Dithioketones,
attached. Ligand can also contain nonbinding
Bis(1,3-Monothioketones), N, O, S, or P atoms. and Poly(1,3-
Monothioketones) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) S--O Valence R--C(.dbd.S)--CR'E"--C(.dbd.O)-- -R"'
where Stabilizer #2: R, R', R", R"', R"", and R""' represent H,
Thiomalonamides NH.sub.2, or any organic functional group
(Thiomalonodiamides), wherein the number of carbon atoms ranges
Bis(thiomalonamides), and from 0 to 40, optionally having halogen
or Polythiomalonamides polarizing or water-insolubilizing/ (S--O
Bidentates, solubilizing groups attached. Ligand can also S--O
Tridentates, contain nonbinding N, O, S, or P atoms. S--O
Tetradentates) S--O Valence RR'--N--C(.dbd.O)--CR"R"'--C(.dbd.S)---
R"" Stabilizer #3: for 2-thioacylacetamides, and
2-Thioacylacetamides, 2- RR'--N--C(.dbd.S)--CR"R"'--C(.dbd.O)--R""
Acylthioacetamides, for 2-acylthioacetamides, where R, R', R",
Bis(2-thioacyl- R"', and R"" represent H, NH.sub.2, or any
acetamides), organic functional group wherein the number
Bis(2acylthio- of carbon atoms ranges from 0 to 40, acetamides),
Poly(2- optionally having halogen or polarizing or
thioacylacetamides), and water-insolubilizing/solubilizing groups
Poly(2-Acylthio- attached. Ligand can also contain acetamides)
nonbinding N, O, S, or P atoms. (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) S--O Valence
RR'--N--C(.dbd.S)--S--C(.dbd.O)--N--R"R"' Stabilizer #4: where R,
R', R", and R"' represent H, NH.sub.2 or Dithiodicarbonic any
organic functional group wherein the Diamides, number of carbon
atoms ranges from 0 to 40, Bis(dithiodicarbonic optionally having
halogen or polarizing or diamides), and water-insolubilizing/solub-
ilizing groups Poly(dithiodicarbonic attached. Ligand can also
contain nonbinding diamides) (S--O N, O, S, or P atoms. Bidentates,
S--O Tridentates, S--O Tetradentates) S--O Valence
(R--O--)(R'--O--)P(.dbd.S)-- Stabilizer #5:
P(.dbd.O)(--O--R')(--O--R'"); Monothiohypophos-
(R--O--)(R'--S--)P(.dbd.S)-- phoric Acids, P(.dbd.O)(--S--R")(--O--
-R"'); or Bis(monothiohypo- (R--S--)(R'--S--)P(.dbd.S)-- phosphoric
acids), and P(.dbd.O)(--S--R")(--S--R"'), Poly(monothiohypo- where
R, R', R", and R"' represent H, NH.sub.2 or phosphoric acids), and
any organic functional group wherein the derivatives thereof number
of carbon atoms ranges from 0 to 40, (S--O Bidentates, optionally
having halogen or polarizing or S--O Tridentates,
water-insolubilizing/solubilizing groups S--O Tetradentates)
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
Note: these ligands are not to be confused with hypophosphorous
acid derivatives (hypophosphites) (R-- O--)R"R"'P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. S--O Valence
(RR'--N--)(R"R'"--N--)P(.dbd.S)(--N-- Stabilizer #6:
R""R""')(--N--R"""R"""'), where R, R', Monothiohypo- R", R"', R"",
R""', R""", and R"""' represent phosphoramides, H, NH.sub.2 or any
organic functional group Bis(monothiohypo- wherein the number of
carbon atoms ranges phosphoramides), and from 0 to 40, optionally
having halogen or Poly(monothiohypo- polarizing or
water-insolubilizing/ phosphoramides) (S--O solubilizing groups
attached. Ligand can also Bidentates, S--O contain nonbinding N, O,
S, or P atoms. Tridentates, S--O Note: these ligands are not to be
confused Tetradentates) with hypophosphorous acid derivatives
(hypophosphites) (R--O--) R"R"'P(.dbd.O) which are very reducing
and therefore unacceptable for stabilization of high valence states
in metal ions. S--O Valence (R--O--)(R'--O--)P(.dbd.S)--NH--
Stabilizer #7: P(.dbd.O)(--O--R")(--O--R"'); Monothioimido-
(R--O--)(R'--S--)P(S)--NH-- diphosphoric Acids,
P(.dbd.O)(--S--R")(--0--R"'); or Monothiohydrazido- (R--S--)(R
'--S--)P(.dbd.S)--NH-- diphosphoric Acids, P(.dbd.O)(--S--R")(--S--
-R"') Bis(monothioimido- for monothioimidodiphosphoric acids,
diphosphoric Acids), and --NH--NH-- derivatives for
Bis(monothiohydrazido- monothiohydrazidodiphosphoric acids, where
diphosphoric Acids), R,R',R", and R"' represent H, NH.sub.2 or any
Poly(monothioimidodi- organic functional group wherein the number
phosphoric Acid), of carbon atoms ranges from 0 to 40,
Poly(monothiohydrazido- optionally having halogen or polarizing or
diphosphoric Acids), water-insolubilizing/solubilizing groups and
derivatives thereof attached. Ligand can also contain nonbinding
(5--O Bidentates, N, O, S, or P atoms. S--O Tridentates, S--O
Tetradentates) S--O Valence (RR'--N--)(R"R"'--N--)P(.dbd.S)--- NH--
Stabilizer #8: P(.dbd.O)(--N--R""R""')(--N--R"""R"""')
Monothioimidodi- for monothiolmidodiphosphoramides, and
phosphoramides, --NH--NH-- derivatives for Monothiohydrazidodi-
monothiohydrazidodiphosphoramides, where phosphoramides, R, R', R",
R"', R"", R""', R""", and R'""" Bis(monothioimidodi- represent H,
NH.sub.2 or any organic functional phosphoramides), group wherein
the number of carbon atoms Bis(monothiohydrazido- ranges from 0 to
40, optionally having diphosphoramides), halogen or polarizing or
water- Poly(monothioimidodi- insolubilizing/solubili- zing groups
attached. phosphoramides), and Ligand can also contain nonbinding
N, O, S, Poly(monothiohydrazido- or P atoms. diphosphoramides)
(5--O Bidentates, 5--O Tridentates, 5--O Tetradentates) S--O
Valence (RR'--N--)(R"R"'--N--)P(.dbd.S)- --S-- Stabilizer #9:
P(.dbd.O)(--N--R""R""')(--N--R"""R"""'), Monothiodi- or (RR
'--N--)(R"R"'--N--)P(.dbd.S)--O-- phosphoramides,
P(.dbd.O)(--N--R""R""')(--N--R"""R"""'), Bis(monothioiphos- where
R, R', R", R"', R"", R""', R""", phoramides), and and R"""'
represent H, NH.sub.2 or any organic Poly(monothiodi- functional
group wherein the number of phosphoramides) (S--O carbon atoms
ranges from 0 to 40, optionally Bidentates, S--O having halogen or
polarizing or water- Tridentates, S--O insolubilizing/solubilizing
groups attached. Tetradentates) Ligand can also contain nonbinding
N, O, S, or P atoms. S--O Valence (R--O--)(R'--O--)P(.dbd.S)--O--
Stabilizer #10: P(.dbd.O)(--O--R")(--O--R'"); Monothiodi-
(R--O--)(R'--O--)P(.dbd.S)-- phosphoric Acids,
S--P(.dbd.O)(--O--R")(--O--R'"); Bis(monothioi-
(R--O--)(R'--O--)P(.dbd.S)-- phosphoric Acids),
O--P(.dbd.O)(--O--R")(--O--R'"); Poly(monothiodi-
(R--O--)(R'--O--)P(.dbd.S)-- phosphoric Acids), and
S--P(.dbd.O)(--O--R")(--O--R'"); or derivatives thereof
(R--S--)(R'--S--)P(.dbd.S)-- (S--O Bidentates,
S--P(.dbd.O)(--S--R")(--S--R'"), S--O Tridentates, where R, R', R",
R"', R"", R""', R""", and S--O Tetradentates) R"""' represent H,
NH.sub.2 or any organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence RR'N.sup.+.dbd.C(OH)(SH), where R and R' Stabilizer #11:
represent H, OH, SH, OR" (R".dbd.C.sub.1-C.sub.30
Monothiocarbamates, alkyl or aryl), SR" (R".dbd.C.sub.1-C.sub.30
alkyl Bis(monothio- or aryl), NH.sub.2 or any organic functional
group carbamates), and wherein the number of carbon atoms ranges
Poly(monothiocarbamates) from 0 to 40, optionally having halogen
(including N- or polarizing or water-insolubilizing/
hydroxymonothio- solubilizing groups attached. Ligand carbamates
and N- can also contain nonbinding N, O, S, mercaptomonothio- or P
atoms. carbamates) (S--O Bidentates, S--O Tridentates, and S--O
Tetradentates) Miscellaneous Valence Hydroxo and oxo ligands bound
directly to Stabilizer #1: the high valence metal ion. Hydroxo and
Oxo Ligands
[0112] N Valence Stabilizer #1: Examples of monoamines (N
monodentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: ammonia; ethylamine; n-dodecylamine; octylamine;
phenylamine; cyclohexylamine; diethylamine; dioctylamine;
diphenylamine; dicyclohexylamine; azetidine; hexamethylenetetramine
(Urotropin); aziridine; azepine; pyrrolidine; benzopyrrolidine;
dibenzopyrrolidine; naphthopyrrolidine; piperidine;
benzopiperidine; dibenzopiperidine; naphthopiperidine;
azacycloheptane (hexamethyleneimine); aminonorbornane;
adamantanamine; aniline; benzylamine; toluidine; phenethylamine;
xylidine; cumidine; naphthylamine; polyalkylamines; polyanilines;
and fluorenediamine.
[0113] N Valence Stabilizer #2: Examples of diamines (N--N
bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hydrazine; phenylhydrazine; 1,1-diphenylhydrazine;
1,2-diphenylhydrazine (hydrazobenzene); methanediamine;
ethylenediamine (1,2-ethanediamine, en); trimethylenediamine
(1,3-propanediamine); putrescine (1,4-butanediamine); cadaverine
(1,5-pentanediamine); hexamethylenediamine (1,6-hexanediamine);
2,3-diaminobutane; stilbenediamine
(1,2-diphenyl-1,2-ethanediamine); cyclohexane-1,2-diamine- ;
cyclopentane-1,2-diamine; 1,3-diazacyclopentane;
1,3-diazacyclohexane; piperazine; benzopiperazine;
dibenzopiperazine; naphthopiperazine; diazepine; thiadiazepine;
oxodiazepine; sparteine (lupinidine);
2-(aminomethyl)azacyclohexane; 2-(aminomethyl)piperidine;
2-(aminomethyl)pyrrolidine; 2-(aminomethyl)azetidine;
2-(2-aminoethyl)aziridine; 1,2-diaminobenzene; benzidine;
bis(2,2'-piperazino)-1,2-ethene; 1,4-diazabicyclo[2.2.2]octane;
naphthylethylenediamine; and 1,2-dianilinoethane.
[0114] N Valence Stabilizer #3: Examples of triamines (N--N
bidentates or N--N tridentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: N-(2-aminoethyl)-1,2-ethanediamine
(dien, 2,2-tri); N-(2-aminoethyl)-1,3-propanediamine (2,3-tri);
N-(3aminopropyl)-1,3-propa- nediamine (3,3-tri, dpt);
N-(3-aminopropyl)-1,4-butanediamine (3,4-tri, spermidine);
N-(2-aminoethyl)-1,4-butanediamine (2,4-tri);
N-(6-hexyl)-1,6-hexanediamine (6,6-tri); 1,3,5-triaminocyclohexane
(tach); 2-(aminomethyl)-1,3-propanediamine (tamm);
2-(aminomethyl)-2-methyl-1,3-propanediamine (tame);
2-(aminomethyl)-2-ethyl-1,3-propanediamine (tamp);
1,2,3-triaminopropane (tap); 2,3-(2-aminoethyl)aziridine;
2,4-(aminomethyl)azetidine; 2,5-(aminomethyl)pyrrolidine;
2,6-(aminomethyl)piperidine; di(2-aminobenzyl)amine;
hexahydro-1,3,5-triazine; hexahydro-2,4,6-trimeth-
yl-1,3,5-triazine; and 1,3,5-tris(aminomethyl)benzene.
[0115] N Valence Stabilizer #4: Examples of tetramines (N--N
bidentates, N--N tridentates, or N--N tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N'-(2-aminoethyl)-1,2-ethanediamine (2,2,2-tet, trien
(triethylenetetramine)); N,N'-(2-aminoethyl)-1,3-propan- ediamine
(2,3,2-tet, entnen); N,N'-(3-aminopropyl)-1,2-ethanediamine
(3,2,3-tet, tnentn);
N-(2-aminoethyl)-N'-(3-aminopropyl)-1,2-ethanediamin- e
(2,2,3-tet); N-(2-aminoethyl)-N'-(3-aminopropyl)-1,3-propanediamine
(3,3,2-tet); N,N'-(3-aminopropyl)-1,3-propanediamine (3,3,3-tet);
N,N'-(3-aminopropyl)-1,4-butanediamine (3,4,3-tet, spermine);
tri(aminomethyl)amine (tren); tri(2-aminoethyl)amine (trtn);
tri(3-aminopropyl)amine (trbn); 2,2-aminomethyl-1,3-propanediamine
(tam); 1,2,3,4-tetraminobutane (tab);
N,N'-(2-aminophenyl)-1,2-ethanediamine; and
N,N'-(2-aminophenyl)-1,3-propanediamine.
[0116] N Valence Stabilizer #5: Examples of pentamines (N--N
bidentates, N--N tridentates, or N--N tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N-[N-(2-aminoethyl)-2-aminoethyl]-N'-(2--
aminoethyl)-1,2-ethanediamine (2,2,2,2-pent, tetren);
N-[N-(3-aminopropyl)-2-aminoethyl]-N'-(3-aminopropyl)-1,2-ethanediamine
(3,2,2,3-pent); N-[N-(3-aminopropyl)-3-aminopropyl]-N
'-(3-aminopropyl)-1,3-propanediamine (3,3,3,3-pent,
caldopentamine);
N-[N-(2-aminobenzyl)-2-aminoethyl]-N'-(2-aminopropyl)-1,2-ethanediamine;
N-[N-(2-aminoethyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine (trenen);
and N-[N-(2-aminopropyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine
(4-Me-trenen).
[0117] N Valence Stabilizer #6: Examples of hexamines (N--N
bidentates, N--N tridentates, N--N tetradentates, or
N--N--N--N--N--N hexadentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to:
N,N'-[N-(2-aminoethyl)-2-aminoethyl]-1,2-ethanediamine
(2,2,2,2,2-hex, linpen);
N,N'-[N-(2-aminoethyl)-3-aminopropyl]-1,2-ethanediamine
(2,3,2,3,2-hex); N,N,N',N'-(2-aminoethyl)-1,2-ethanediamine
(penten, ten); N,N,N',N'-(2-aminoethyl)-1-methyl-1,2-ethanediamine
(tpn, R-5-Me-penten); N,N,N',N'-(2-aminoethyl)-1,3-propanediamine
(ttn); N,N,N',N'-(2-aminoethyl)-1,4-butanediamine (tbn);
N,N,N',N'-(2-aminoethyl- )-1,3-dimethyl-1,3-propanediamine
(R,R-tptn, R,S-tptn);
N-(2-aminoethyl)-2,2-[N-(2-aminoethyl)aminomethyl-1-propaneamine
(sen); and
N-(3-aminopropyl)-2,2-[N-(3-aminopropyl)aminomethyl-1-propaneamine
(stn).
[0118] N Valence Stabilizer #7a: Examples of 5-membered
heterocyclic rings containing one nitrogen atom (N monodentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrole,
oxazole, isoxazole, thiazole, isothiazole, azaphosphole,
benzopyrroline, benzopyrrole (indole), benzoxazole, benzisoxazole,
benzothiazole, benzisothiazole, benzazaphosphole, dibenzopyrroline,
dibenzopyrrole (carbazole), dibenzoxazole, dibenzisoxazole,
dibenzothiazole, dibenzisothiazole, naphthopyrroline,
naphthopyrrole, naphthoxazole, naphthisoxazole, naphthothiazole,
naphthisothiazole, naphthazaphosphole, and polypyrroles.
[0119] N Valence Stabilizer #7b: Examples of 5-membered
heterocyclic rings containing two nitrogen atoms (N monodentates or
N--N bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: pyrazoline, imidazoline, imidazole (ia), pyrazole,
oxadiazole, thiadiazole, diazaphosphole, benzopyrazoline,
benzimidazoline, benzimidazole (azindole)(bia)(bz), benzopyrazole
(indazole), benzothiadiazole (piazthiole), benzoxadiazole
(benzofurazan), naphthopyrazoline, naphthimidazoline,
naphthimidazole, naphthopyrazole, naphthoxadiazole,
naphthothiadiazole, polybenzimidazole, and polyimidazoles (e.g.
polyvinylimidazole (pvi)).
[0120] N Valence Stabilizer #7c: Examples of 5-membered
heterocyclic rings containing three nitrogen atoms (N monodentates,
N--N bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: triazole, oxatriazole, thiatriazole, benzotriazole
(bta), tolyltriazole (tt), naphthotriazole, and
triazolophthalazine.
[0121] N Valence Stabilizer #7d: Examples of 5-membered
heterocyclic rings containing four nitrogen atoms (N monodentates
or N--N bidentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: tetrazole.
[0122] N Valence Stabilizer #8a: Examples of 6-membered
heterocyclic rings containing one nitrogen atom (N monodentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: pyridine, picoline, lutidine, .gamma.-collidine,
oxazine, thiazine, azaphosphorin, quinoline, isoquinoline,
benzoxazine, benzothiazine, benzazaphosphorin, acridine,
phenanthridine, phenothiazine (dibenzothiazine), dibenzoxazine,
dibenzazaphosphorin, benzoquinoline (naphthopyridine),
naphthoxazine, naphthothiazine, naphthazaphosphorin, and
polypyridines.
[0123] N Valence Stabilizer #8b: Examples of 6-membered
heterocyclic rings containing two nitrogen atoms (N monodentates or
N--N bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: pyrazine, pyridazine, pyrimidine, oxadiazine,
thiadiazine, diazaphosphorin, quinoxaline (benzopyrazine),
cinnoline (benzo[c]pyridazine), quinazoline (benzopyrimidine),
phthalazine (benzo[d]pyridazine), benzoxadiazine, benzothiadiazine,
phenazine (dibenzopyrazine), dibenzopyridazine, naphthopyrazine,
naphthopyridazine, naphthopyrimidine, naphthoxadiazine,
naphthothiadiazine, and polyquinoxalines.
[0124] N Valence Stabilizer #8c: Examples of 6-membered
heterocyclic rings containing three nitrogen atoms (N monodentates
or N--N bidentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 1,3,5-triazine, 1,2,3-triazine,
benzo-1,2,3-triazine, naphtho-1,2,3-triazine, oxatriazine,
thiatriazine, melamine, and cyanuric acid.
[0125] N Valence Stabilizer #8d: Examples of 6-membered
heterocyclic rings containing four nitrogen atoms (N monodentates
or N--N bidentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: tetrazine.
[0126] N Valence Stabilizer #9a: Examples of 5-membered
heterocyclic rings containing one nitrogen atom and having at least
one additional nitrogen atom binding site not contained in a ring
(N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(aminomethyl)-3-pyrroline; 2,5-(aminomethyl)-3-pyrroline;
2-(aminomethyl)pyrrole; 2,5-(aminomethyl)pyrrole;
3-(aminomethyl)isoxazol- e; 2-(aminomethyl)thiazole;
3-(aminomethyl)isothiazole; 2-(aminomethyl)indole;
2-aminobenzoxazole; 2-aininobenzothiazole (abt);
1,8-diaminocarbazole; 2-amino-6-methyl-benzothiazole (amebt);
2-amino-6-methoxybenzothiazole (ameobt), and
1,3-diiminoisoindoline.
[0127] N Valence Stabilizer #9b: Examples of 5-membered
heterocyclic rings containing two nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-aminoimidazoline;
1-(3-aminopropyl)imidazoline; 2-aminoimidazole;
1-(3-aminopropyl)imidazol- e; 4-(2-aminoethyl)imidazole
[histamine]; 1-alkyl-4-(2-aminoethyl)imidazol- e;
3-(2-aminoethyl)pyrazole; 3,5-(2-aminoethyl)pyrazole;
1-(aminomethyl)pyrazole; 2-aminobenzimidazole;
7-(2-aminoethyl)benzimidaz- ole; 1-(3-aminopropyl)benzimidazole;
3-(2-aminoethyl)indazole; 3,7-(2-aminoethyl)indazole;
1-(aminomethyl)indazole; 7-aminobenzothiadiazole;
4-(2-aminoethyl)benzothiadiazole; 7-aminobenzoxadiazole;
4-(2-aminoethyl)benzoxadiazole;
ethylenediaminetetra(1-pyrazolylmethane) [edtp];
methylenenitrilotris(2-(- 1-methyl)benzimidazole) [mntb]
[tris(1-methyl-2-benzimidazolylmethane)amin- e];
bis(alkyl-1-pyrazolylmethane)amine;
bis(alkyl-2-(1-pyrazolyl)ethane)am- ine;
bis(N,N-(2-benzimidazolyl)-2-aminoethane)(2-benzimidazolylmethane)ami-
ne; bis(1-(3,5-dimethyl)pyrazolylmethane)phenylamine;
tris(2-(1-(3,5-dimethyl)pyrazolyl)ethane)amine;
5-(dimethylamino)pyrazole- ; 5-(dimethylaminomethyl)pyrazole;
2-amino-1,3,4-thiadiazole; and 1-(2-aminoethyl)imidazoline.
[0128] N Valence Stabilizer #9c: Examples of 5-membered
heterocyclic rings containing three nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N--N Tridentates, N--N--N--N
Tetradentates, or N--N--N--N--N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
3-amino-1,2,4-triazole (ata); 3,5-diamino-1,2,4-triazole (dat);
5-amino-1,2,4-triazole; 3-(2-aminoethyl)-1,2,4-triazole;
5-(2-aminoethyl)-1,2,4-triazole; 3,5-(2-aminoethyl)-1,2,4-triazole;
1-(aminomethyl)-1,2,4-triazole;
3,5-(aminomethyl)-4-amino-1,2,4-triazole;
4-(2-aminoethyl)-1,2,3-triazole; 5-(2-aminoethyl)-1,2,3-triazole;
7-aminobenzotriazole; 1-(aminomethyl)-1,2,3-triazole;
1-(2-aminoethyl)-1,2,3-triazole; 4-(3-aminopropyl)benzotriazole;
N-(benzotriazolylalkyl)amine; dibenzotriazole-1-ylalkylamine;
bis(5-amino-1,2,4-triazol-3-yl);
bis(5-amino-1,2,4-triazol-3-yl)alkanes; and
1-(aminomethyl)benzotriazole.
[0129] N Valence Stabilizer #9d: Examples of 5-membered
heterocyclic rings containing four nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 5-(2-aminoethyl)-1H-tet-
razole; 1-(aminomethyl)-1H-tetrazole; and
1-(2-aminoethyl)-1H-tetrazole.
[0130] N Valence Stabilizer #10a: Examples of 6-membered
heterocyclic rings containing one nitrogen atom and having at least
one additional nitrogen atom binding site not contained in a ring
(N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-aminopyridine;
2,6-diaminopyridine; 2-(aminomethyl)pyridine;
2,6-(aminomethyl)pyridine; 2,6-(aminoethyl)pyridine;
2-amino-4-picoline; 2,6-diamino-4-picoline; 2-amino-3,5-lutidine;
2-aminoquinoline; 8-aminoquinoline; 2-aminoisoquinoline;
acriflavine; 4-aminophenanthridine; 4,5-(aminomethyl)phenothiazine;
4,5-(aminomethyl)dibenzoxazine; 10-amino-7,8-benzoquinoline;
bis(2-pyridylmethane)amine; tris(2-pyridyl)amine;
bis(4(2-pyridyl)-3-azab- utane)amine;
bis(N,N-(2-(2-pyridyl)ethane)aminomethane)amine;
4-(N,N-dialkylaminomethyl)morpholine; 6-aminonicotinic acid;
8-aminoacridine; and 2-hydrazinopyridine.
[0131] N Valence Stabilizer #10b: Examples of 6-membered
heterocyclic rings containing two nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-aminopyrazine;
2,6-diaminopyrazine; 2-(aminomethyl)pyrazine;
2,6-(aminomethyl)pyrazine; 3-(aminomethyl)pyridazine;
3,6-(aminomethyl)pyridazine; 3,6-(2-aminoethyl)pyridazine;
1-aminopyridazine; 1-(aminomethyl)pyridazin- e; 2-aminopyrimidine;
1-(2-aminoethyl)pyrimidine; 2-aminoquinoxaline;
2,3-diaminoquinoxaline; 2-aminocinnoline; 3-aminocinnoline;
3-(2-aminoethyl)cinnoline; 3,8-(2-aminoethyl)cinnoline;
2-aminoquinazoline; 1-(2-aminoethyl)quinazoline;
1-aminophthalazine; 1,4-(2-aminoethyl)phthalazine;
1,8-(aminomethyl)phenazine; 2-amino-4,6-dimethylpyrimidine (admp);
dihydralazine; and hydralazine.
[0132] N Valence Stabilizer #10c: Examples of 6-membered
heterocyclic rings containing three nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-amino-1,3,5-triazine;
2-(aminomethyl)-1,3,5-triazine; 2,6-(aminomethyl)-1,3,5-triazine;
1-(3-aminopropyl)-1,3,5-triazine;
1,5-(3-aminopropyl)-1,3,5-triazine, polymelamines; melamine; and
altretamine.
[0133] N Valence Stabilizer #10d: Examples of 6-membered
heterocyclic rings containing four nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
3,6-(2-aminoethyl)-1,2,4,5-tetrazine;
3,6-(1,3-diamino-2-propyl)-1,2,4,5-- tetrazine; and
4,6-(aminomethyl)-1,2,3,5-tetrazine.
[0134] N Valence Stabilizer #11a: Examples of 5-membered
heterocyclic rings containing one nitrogen atom and having at least
one additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-3-pyrroline; 2,2'-bi-2-pyrroline;
2,2'-bi-1-pyrroline; 2,2'-bipyrrole; 2,2',2"-tripyrrole;
3,3'-biisoxazole; 2,2'-bioxazole; 3,3'-biisothiazole;
2,2'-bithiazole; 2,2'-biindole; 2,2'-bibenzoxazole;
2,2'-bibenzothiazole; bilirubin; biliverdine; and 7-azaindole.
[0135] N Valence Stabilizer #11b: Examples of 5-membered
heterocyclic rings containing two nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-2-imidazoline [2,2'-bi-2-imidazolinyl][bi-
md]; 2,2'-biimidazole [2,2'-biimidazolyl][biimH.sub.2];
5,5'-bipyrazole; 3,3'-bipyrazole; 4,4'-bipyrazole
[4,4'-bipyrazolyl][bpz]; 2,2'-bioxadiazole; 2,2'-bithiadiazole;
2,2'-bibenzimidazole; 7,7'-biindazole; 5,5'-bibenzofurazan;
5,5'-bibenzothiadiazole; bis-1,2-(2=benzimidazole)ethane;
bis(2-benzimidazole)methane; 1,2-(2-imidazolyl)benzene;
2-(2-thiazolyl)benzimidazole; 2-(2-imidazolyl)benzimidazole;
benzimidazotriazine; 4-azabenzimidazole; and
2,6-bis(2-benzimidazolyl)pyridine.
[0136] N Valence Stabilizer #11c: Examples of 5-membered
heterocyclic rings containing three nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 5,5'-bi-1,2,4-triazole [btrz];
3,3'-bi-1,2,4-triazole; 1,1'-bi-1,2,4-triazole;
1,1'-bi-1,2,3-triazole; 5,5'-bi-1,2,3-triazole;
7,7'-bibenzotriazole; 1,1'-bibenzotriazole;
bis(pyridyl)aminotriazole (pat); and 8-azaadenine.
[0137] N Valence Stabilizer #11d: Examples of 5-membered
heterocyclic rings containing four nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 5,5'-bi-1H-tetrazole; and 1,1'-bi-1H-tetrazole.
[0138] N Valence Stabilizer #12a: Examples of 6-membered
heterocyclic rings containing one nitrogen atom and having at least
one additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bipyridine [bipy]; 2,2',2"-tripyridine
[terpyridine] [terpy]; 2,2',2",2'"-tetrapyridine [tetrapy];
6,6'-bi-2-picoline; 6,6'-bi-3-picoline; 6,6'-bi-4-picoline;
6,6'-bi-2,3-lutidine; 6,6'-bi-2,4-lutidine; 6,6'-bi-3,4-lutidine;
6,6'-bi-2,3,4-collidine; 2,2'-biquinoline; 2,2'-biisoquinoline;
3,3'-bibenzoxazine; 3,3'-bibenzothiazine; 1,10-phenanthroline
[phen]; 1,8-naphthyridine; bis-1,2-(6-(2,2'-bipyridyl))ethane;
bis-1,3-(6-(2,2'-bipyridyl))propane; 3,5-bis(3-pyridyl)pyrazole;
3,5-bis(2-pyridyl)triazole; 1,3-bis(2-pyridyl)-1,3,5-triazine;
1,3-bis(2-pyridyl)-5-(3-pyridyl)-1,3,5-triazine;
2,7-(N,N'-di-2-pyridyl)d- iaminobenzopyiroline;
2,7-(N,N'-di-2-pyridyl)diaminophthalazine;
2,6-di-(2-benzothiazolyl)pyridine; triazolopyrimidine;
2-(2-pyridyl)imidazoline; 7-azaindole; i-(2-pyridyl)pyrazole;
(1-imidazolyl)(2-pyridyl)methane;
4,5-bis(N,N'-(2-(2-pyridyl)ethyl)iminom- ethyl)imidazole;
bathophenanthroline; 4-(2-benzimidazolyl)quinoline;
1,2-bis(2-pyridyl)ethane; 4,4'-diphenyl-2,2'-dipyridyl;
neocuproine; nicotine; and nornicotine.
[0139] N Valence Stabilizer #12b: Examples of 6-membered
heterocyclic rings containing two nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bipyrazine; 2,2',2"-tripyrazine;
6,6'-bipyridazine; bis(3-pyridazinyl)methane;
1,2-bis(3-pyridazinyl)ethan- e; 2,2'-bipyrimidine;
2,2'-biquinoxaline; 8,8'-biquinoxaline; bis(3-cinnolinyl)methane;
bis(3-cinnolinyl)ethane; 8,8'-bicinnoline; 2,2'-biquinazoline;
4,4'-biquinazoline; 8,8'-biquinazoline; 2,2'-biphthalazine;
1,1'-biphthalazine; 2-(2-pyridyl)benzimidazole; 8-azapurine;
purine; adenine; guanine; hypoxanthine;
2,6-bis(N,N'-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine;
2-(N-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine; adenine
(aminopurine); purine; and 2,3-bis(2-pyridyl)pyrazine.
[0140] N Valence Stabilizer #12c: Examples of 6-membered
heterocyclic rings containing three nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1,3,5-triazine; 2,2',2"-tri-1,3,5-triazine;
4,4'-bi-1,2,3-triazine; and 4,4'-bibenzo-1,2,3-triazine;
2,4,6-tris(2-pyridyl)-1,3,5-triazine; and benzimidazotriazines.
[0141] N Valence Stabilizer #12d: Examples of 6-membered
heterocyclic rings containing four nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 3,3'-bi-1,2,4,5-tetrazine; and
4,4'-bi-1,2,3,5-tetrazine.
[0142] N Valence Stabilizer #13a: Examples of two-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein both
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diazacyclobutane ([4]aneN.sub.2); diazacyclopentane
([5]aneN.sub.2); diazacyclohexane ([6]aneN.sub.2);
diazacycloheptane ([7]aneN.sub.2); diazacyclooctane
([8]aneN.sub.2); piperazine; benzopiperazine; diazacyclobutene
([4]eneN.sub.2); diazacyclopentene ([5]eneN.sub.2);
diazacyclohexene ([6]eneN.sub.2); diazacycloheptene
([7]eneN.sub.2); diazacyclooctene ([8]eneN.sub.2);
diazacyclobutadiene ([4]dieneN.sub.2); diazacyclopentadiene
([5]dieneN.sub.2); diazacyclohexadiene ([6]dieneN.sub.2);
diazacycloheptadiene ([7]dieneN.sub.2); and diazacyclooctadiene
([8]dieneN.sub.2).
[0143] N Valence Stabilizer #13b: Examples of three-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: triazacyclohexane (including
hexahydro-1,3,5-triazine)([6]aneN.sub.3); triazacycloheptane
([7]aneN.sub.3); triazacyclooctane ([8]aneN.sub.3);
triazacyclononane ([9]aneN.sub.3); triazacyclodecane
([10]aneN.sub.3); triazacycloundecane ([11]aneN.sub.3);
triazacyclododecane ([12]aneN.sub.3); triazacyclohexene
([6]eneN.sub.3); triazacycloheptene ([7]eneN.sub.3);
triazacyclooctene ([8]eneN.sub.3); triazacyclononene
([9]eneN.sub.3); triazacyclodecene ([10]eneN.sub.3);
triazacycloundecene ([11]eneN.sub.3); triazacyclododecene
([12]eneN.sub.3); triazacyclohexatriene ([6]trieneN.sub.3);
triazacycloheptatriene ([7]trieneN.sub.3); triazacyclooctatriene
([8]trieneN.sub.3); triazacyclononatriene ([9]trieneN.sub.3);
triazacyclodecatriene ([10]trieneN.sub.3); triazacycloundecatriene
([11]trieneN.sub.3); and triazacyclododecatriene
([12]trieneN.sub.3).
[0144] N Valence Stabilizer #13c: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tetraazacyclooctane ([8]aneN.sub.4);
tetraazacyclononane ([9]aneN.sub.4); tetraazacyclodecane
([10]aneN.sub.4); tetraazacycloundecane ([11]aneN.sub.4);
tetraazacyclododecane ([12]aneN.sub.4); tetraazacyclotridecane
([13]aneN.sub.4); tetraazacyclotetradecane ([14]aneN.sub.4);
tetraazacyclopentadecane ([15]aneN.sub.4); tetraazacyclohexadecane
([16]aneN.sub.4); tetraazacycloheptadecane ([17]aneN.sub.4);
tetraazacyclooctadecane ([18]aneN.sub.4); tetraazacyclononadecane
([19]aneN.sub.4); tetraazacycloeicosane ([20]aneN.sub.4);
tetraazacyclooctadiene ([8]dieneN.sub.4); tetraazacyclononadiene
([9]dieneN.sub.4); tetraazacyclodecadiene ([10]dieneN.sub.4);
tetraazacycloundecadiene ([11]dieneN.sub.4);
tetraazacyclododecadiene ([12]dieneN.sub.4);
tetraazacyclotridecadiene ([13]dieneN.sub.4);
tetraazacyclotetradecadiene ([14]dieneN.sub.4);
tetraazacyclopentadecadie- ne ([15]dieneN.sub.4);
tetraazacyclohexadecadiene ([16]dieneN.sub.4);
tetraazacycloheptadecadiene ([17]dieneN.sub.4);
tetraazacyclooctadecadien- e ([18]dieneN.sub.4);
tetraazacyclononadecadiene ([19]dieneN.sub.4);
tetraazacycloeicosadiene ([20]dieneN.sub.4);
tetraazacyclooctatetradiene ([8]tetradieneN.sub.4);
tetraazacyclononatetradiene ([9]tetradieneN.sub.4);
tetraazacyclodecatetradiene ([10]tetradieneN.sub.4);
tetraazacycloundecatetradiene ([11]tetradieneN.sub.4);
tetraazacyclododecatetradiene ([12]tetradieneN.sub.4);
tetraazacyclotridecatetradiene ([13]tetradieneN.sub.4);
tetraazacyclotetradecatetradiene ([14]tetradieneN.sub.4);
tetraazacyclopentadecatetradiene ([15]tetradieneN.sub.4);
tetraazacyclohexadecatetradiene ([16]tetradieneN.sub.4);
tetraazacycloheptadecatetradiene ([17]tetradieneN.sub.4);
tetraazacyclooctadecatetradiene ([18]tetradieneN.sub.4);
tetraazacyclononadecatetradiene ([19]tetradieneN.sub.4); and
tetraazacycloeicosatetradiene ([20]tetradieneN.sub.4).
[0145] N Valence Stabilizer #13d: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexaazacyclododecane ([12]aneN.sub.6); hexaazacyclotridecane
([13]aneN.sub.6); hexaazacyclotetradecane ([14]aneN.sub.6);
hexaazacyclopentadecane ([15]aneN.sub.6); hexaazacyclohexadecane
([16]aneN.sub.6); hexaazacycloheptadecane ([17]aneN.sub.6);
hexaazacyclooctadecane ([18]aneN.sub.6); hexaazacyclononadecane
([19]aneN.sub.6); hexaazacycloeicosane ([20]aneN.sub.6);
hexaazacycloheneicosane ([21]aneN.sub.6); hexaazacyclodocosane
([22]aneN.sub.6); hexaazacyclotricosane ([23]aneN.sub.6);
hexaazacyclotetracosane ([24]aneN.sub.6); hexaazacyclododecatriene
([12]trieneN.sub.6); hexaazacyclotridecatriene ([13]trieneN.sub.6);
hexaazacyclotetradecatriene ([14]trieneN.sub.6);
hexaazacyclopentadecatri- ene ([15]trieneN.sub.6);
hexaazacyclohexadecatriene ([16]trieneN.sub.6);
hexaazacycloheptadecatriene ([17]trieneN.sub.6);
hexaazacyclooctadecatrie- ne ([18]trieneN.sub.6);
hexaazacyclononadecatriene ([19]trieneN.sub.6);
hexaazacycloeicosatriene ([20]trieneN.sub.6);
hexaazacycloheneicosatriene ([21]trieneN.sub.6);
hexaazacyclodocosatriene ([22]trieneN.sub.6);
hexaazacyclotricosatriene ([23]trieneN.sub.6); and
hexaazacyclotetracosatriene ([24]trieneN.sub.6).
[0146] N Valence Stabilizer #13e: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
octaazacyclohexadecane ([16]aneN.sub.8); octaazacycloheptadecane
([17]aneN.sub.8); octaazacyclooctadecane ([18]aneN.sub.8);
octaazacyclononadecane ([19]aneN.sub.8); octaazacycloeicosane
([20]aneN.sub.8); octaazacycloheneicosane ([21]aneN.sub.8);
octaazacyclodocosane ([22]aneN.sub.8); octaazacyclotricosane
([23]aneN.sub.8); octaazacyclotetracosane ([24]aneN.sub.8);
octaazacyclohexadecatetradiene ([16]tetradieneN.sub.8);
octaazacycloheptadecatetradiene ([17]tetradieneN.sub.8);
octaazacyclooctadecatetradiene ([18]tetradieneN.sub.8);
octaazacyclononadecatetradiene ([19]tetradieneN.sub.8);
octaazacycloeicosatetradiene ([20]tetradieneN.sub.8);
octaazacycloheneicosatetradiene ([21]tetradieneN.sub.8);
octaazacyclodocosatetradiene ([22]tetradieneN.sub.8);
octaazacyclotricosatetradiene ([23]tetradieneN.sub.8); and
octaazacyclotetracosatetradiene ([24]tetradieneN.sub.8).
[0147] N Valence Stabilizer #13f: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchratcs) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
decaazacycloeicosane ([20]aneN.sub.0); decaazacycloheneicosane
([21]aneN.sub.10); decaazacyclodocosane ([22]aneN.sub.10);
decaazacyclotricosane ([23]aneN.sub.10); decaazacyclotetracosane
([24]aneN.sub.10); decaazacyclopentacosane ([25]aneN.sub.10);
decaazacyclohexacosanc ([26]aneN.sub.10); decaazacycloheptacosane
([27]aneN.sub.10); decaazacyclooctacosane ([28]aneN.sub.10);
decaazacyclononacosane ([29]aneN.sub.10); decaazacyclotriacontane
([30]aneN.sub.10); decaazacycloeicosapentadiene
([20]pentadieneN.sub.10); decaazacycloheneicosapentadiene
([21]pentadieneN.sub.10); decaazacyclodocosapentadiene
([22]pentadieneN.sub.10); decaazacyclotricosapentadiene
([23]pentadieneN.sub.10); decaazacyclotetracosapentadiene
([24]pentadieneN.sub.10); decaazacyclopentacosapentadiene
([25]pentadieneN.sub.10); decaazacyclohexacosapentadiene
([26]pentadieneN.sub.10); decaazacycloheptacosapentadiene
([27]pentadieneN.sub.10); decaazacyclooctacosapentadiene
([28]pentadieneN.sub.10); decaazacyclononacosapentadiene
([29]pentadieneN.sub.10); and decaazacyclotriacontapentadiene
([30]pentadieneN.sub.10).
[0148] N Valence Stabilizer #14a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of nitrogen and are contained in
component 5-membered heterocyclic rings (N--N Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
porphyrins (including tetraphenylporphine (tpp); "picket fence"
porphyrins, "picket tail" porphyrins, "bispocket" porphyrins,
"capped" porphyrins, cyclophane porphyrins, "pagoda" porphyrins,
"pocket" porphyrins, "pocket tail" porphyrins, cofacial
diporphyrins, "strapped" porphyrins, "hanging base" porphyrins,
bridged porphyrins, chelated mesoporphyrins, homoporphyrins,
chlorophylls, and pheophytins); porphodimethanes; porphyrinogens;
chlorins; bacteriochlorins; isobacteriochlorins; corroles; corrins
and corrinoids; didehydrocorrins; tetradehydrocorrins;
hexadehydrocorrins; octadehydrocorrins; tetraoxazoles;
tetraisooxazoles; tetrathiazoles; tetraisothiazoles;
tetraazaphospholes; tetraimidazoles; tetrapyrazoles;
tetraoxadiazoles; tetrathiadiazoles; tetradiazaphospholes;
tetratriazoles; tetraoxatriazoles; tetrathiatriazoles;
coproporphyrin; etioporphyrin; and hematoporphyrin.
[0149] N Valence Stabilizer #14b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of nitrogen and are contained in
component 5-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: hexaphyrins
(hexapyrroles); hexaoxazoles; hexaisooxazoles; hexathiazoles;
hexaisothiazoles; hexaazaphospholes; hexaimidazoles; hexapyrazoles;
hexaoxadiazoles; hexathiadiazoles; hexadiazaphospholes;
hexatriazoles; hexaoxatriazoles; and hexathiatriazoles.
[0150] N Valence Stabilizer #14c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of nitrogen and are contained in
component 5-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: octaphyrins
(octapyrroles); octaoxazoles; octaisooxazoles; octathiazoles;
octaisothiazoles; octaazaphospholes; octaimidazoles; octapyrazoles;
octaoxadiazoles; octathiadiazoles; octadiazaphospholes;
octatriazoles; octaoxatriazoles; and octathiatriazoles.
[0151] N Valence Stabilizer #14d: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of nitrogen and are contained in
component 5-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: decaphyrins
(decapyrroles); decaoxazoles; decaisooxazoles; decathiazoles;
decaisothiazoles; decaazaphospholes; decaimidazoles; decapyrazoles;
decaoxadiazoles; decathiadiazoles; decadiazaphospholes;
decatriazoles; decaoxatriazoles; and decathiatriazoles.
[0152] N Valence Stabilizer #15a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tetradentates) that meet the requirements for use as
"wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: porphyrazines;
octahydrodiazaporphyrins; phthalocyanines; naphthalocyanines;
anthracocyanines; and tetraazaporphyrins
[0153] N Valence Stabilizer #15b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazahexaphyrins; tetraazahexaphyrins;
hexaazahexaphyrins; diazahexapyrazoles; tetraazahexapyrazoles;
hexaazahexapyrazoles; diazahexaimidazoles; tetraazahexaimidazoles;
and hexaazahexaimidazoles.
[0154] N Valence Stabilizer #15c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazaoctaphyrins; tetraazaoctaphyrins;
hexaazaoctaphyrins; octaazaoctaphyrins; diazaoctapyrazoles;
tetraazaoctapyrazoles; hexaazaoctapyrazoles; octaazaoctapyrazoles;
diazaoctaimidazoles; tetraazaoctaimidazoles; hexaazaoctaimidazoles;
and octaazaoctaimidazoles.
[0155] N Valence Stabilizer #15d: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazadecaphyrins; tetraazadecaphyrins;
hexaazadecaphyrins; octaazadecaphyrins; decaazadecaphyrins;
diazadecapyrazoles; tetraazadecapyrazoles; hexaazadecapyrazoles;
octaazadecapyrazoles; decaazadecapyrazoles; diazadecaimidazoles;
tetraazadecaimidazoles; hexaazadecaimidazoles;
octaazadecaimidazoles; and decaazadecaimidazoles.
[0156] N Valence Stabilizer #16a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of nitrogen and are contained in
component 6-membered heterocyclic rings (N--N Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
cyclotetrapyridines; cyclotetraoxazines; cyclotetrathiazines;
cyclotetraphosphorins; cyclotetraquinolines; cyclotetrapyrazines;
cyclotetrapyridazines; cyclotetrapyrimidines;
cyclotetraoxadiazines; cyclotetrathiadiazines;
cyclotetradiazaphosphorins; cyclotetraquinoxalines;
cyclotetratriazines; cyclotetrathiatriazines; and
cyclotetraoxatriazines.
[0157] N Valence Stabilizer #16b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of nitrogen and are contained in
component 6-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: cyclosexipyridines;
cyclosexioxazines; cyclosexithiazines; cyclosexiphosphorins;
cyclosexiquinolines; cyclosexipyrazines; cyclosexipyridazines;
cyclosexipyrimidines; cyclosexioxadiazines; cyclosexithiadiazines;
cyclosexidiazaphosphorins cyclosexiquinoxalines;
cyclosexitriazines; cyclosexithiatriazines; and
cyclosexioxatriazines.
[0158] N Valence Stabilizer #16c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of nitrogen and are contained in
component 6-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: cyclooctapyridines;
cyclooctaoxazines; cyclooctathiazines; cyclooctaphosphorins;
cyclooctaquinolines; cyclooctapyrazines; cyclooctapyridazines;
cyclooctapyrimidines; cyclooctaoxadiazines; cyclooctathiadiazines;
cyclooctadiazaphosphorins; cyclooctaquinoxalines;
cyclooctatriazines; cyclooctathiatriazines; and
cyclooctaoxatriazines.
[0159] N Valence Stabilizer #16d: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of nitrogen and are contained in
component 6-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: cyclodecapyridines;
cyclodecaoxazines; cyclodecathiazines; cyclodecaphosphorins;
cyclodecaquinolines; cyclodecapyrazines; cyclodecapyridazines;
cyclodecapyrimidines; cyclodecaoxadiazines; cyclodecathiadiazines;
cyclodecadiazaphosphorins; cyclodecaquinoxalines;
cyclodecatriazines; cyclodecathiatriazines; and
cyclodecaoxatriazines.
[0160] N Valence Stabilizer #17a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tetradentates) that meet the requirements for use as
"wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: diazacyclotetrapyridine- s;
tetraazacyclotetrapyridines; diazacyclotetraquinolines;
tetraazacyclotetraquinolines; diazacyclotetrapyrazines;
tetraazacyclotetrapyrazines; diazacyclotetrapyridazines;
tetraazacyclotetrapyridazines; diazacyclotetrapyrimidines;
tetraazacyclotetrapyrimidines; diazacyclotetratriazines; and
tetraazacyclotetratriazines.
[0161] N Valence Stabilizer #17b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazacyclosexipyridines; triazacyclosexipyridines;
diazacyclosexiquinolines; triazacyclosexiquinolines;
diazacyclosexipyrazines; triazacyclosexipyrazines;
diazacyclosexipyridazines; triazacyclosexipyridazines;
diazacyclosexipyrimidines; triazacyclosexipyrimidines;
diazacyclosexitriazines; and triazacyclosexitriazines.
[0162] N Valence Stabilizer #17c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazacyclooctapyridines; tetraazacyclooctapyridines;
diazacyclooctaquinolines; tetraazacyclooctaquinolines;
diazacyclooctapyrazines; tetraazacyclooctapyrazines;
diazacyclooctapyridazines; tetraazacyclooctapyridazines;
diazacyclooctapyrimidines; tetraazacyclooctapyrimidines;
diazacyclooctatriazines; and tetraazacyclooctatriazines.
[0163] N Valence Stabilizer #17d: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazacyclodecapyridines; pentaazacyclodecapyridines;
diazacyclodecaquinolines; pentaazacyclodecaquinolines;
diazacyclodecapyrazines; pentaazacyclodecapyrazines;
diazacyclodecapyridazines; pentaazacyclodecapyridazines;
diazacyclodecapyrimidines; pentaazacyclodecapyrimidines;
diazacyclodecatriazines; and pentaazacyclodecatriazines.
[0164] N Valence Stabilizer #18: Examples of amidines and
diamidines (N--N bidentates or N--N Tetradentates) that meet the
requirements for use as ""wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N'-dimethylformamidine; N,N'-diethylformamidine- ;
N,N'-diisopropylformamidine; N,N'-dibutylformamidine;
N,N'-diphenylformamidine; N,N'-dibenzylformamidine;
N,N'-dinaphthylformamidine; N,N'-dicyclohexylformamidine;
N,N'-dinorbornylformamidine; N,N'-diadamantylformamidine;
N,N'-dianthraquinonylformamidine; N,N'-dimethylacetamidine;
N,N'-diethylacetamidine; N,N'-diisopropylacetamidine;
N,N'-dibutylacetamidine; N,N'-diphenylacetamidine;
N,N'-dibenzylacetamidine; N,N'-dinaphthylacetamidine;
N,N'-dicyclohexylacetamidine; N,N'-dinorbornylacetamidine;
N,N'-diadamantylacetamidine; N,N'-dimethylbenzamidine;
N,N'-diethylbenzamidine; N,N'-diisopropylbenzamidine;
N,N'-dibutylbenzamidine; N,N'-diphenylbenzamidine;
N,N'-dibenzylbenzamidine; N,N'-dinaphthylbenzamidine;
N,N'-dicyclohexylbenzamidine; N,N'-dinorbornylbenzamidine;
N,N'-diadamantylbenzamidine; N,N'-dimethyltoluamidine;
N,N'-diethyltoluamidine; N,N'-diisopropyltoluamidine;
N,N'-dibutyltoluamidine; N,N'-diphenyltoluamidine;
N,N'-dibenzyltoluamidine; N,N'-dinaphthyltoluamidine;
N,N'-dicyclohexyltoluamidine; N,N'-dinorbornyltoluamidine;
N,N'-diadamantyltoluamidine; oxalic diamidine; malonic diamidine;
succinic diamidine; glutaric diamidine; adipic diamidine; pimelic
diamidine; suberic diamidine; phthalic diamidine; terephthalic
diamidine; isophthalic diamidine; piperazine diamidine;
2-iminopyrrolidine; 2-iminopiperidine; amidinobenzamide;
benzamidine; chloroazodin; and debrisoquin.
[0165] N Valence Stabilizer #19: Examples of biguamides
(imidodicarbonimidic diamides), biguanidines, imidotricarbonimidic
diamides, imidotetracarbonimidic diamides, dibiguamides,
bis(biguanidines), polybiguamides, and poly(biguanidines) (N--N
bidentates, N--N tridentates, N--N tetradentates, and N--N
hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: biguamide (bigH); biguanidine, methylbiguamide;
ethylbiguamide; isopropylbiguamide; butylbiguamide;
benzylbiguamide; phenylbiguamide; tolylbiguamide;
naphthylbiguamide; cyclohexylbiguamide; norbornylbiguamide;
adamantylbiguamide; dimethylbiguamide; diethylbiguamide;
diisopropylbiguamide; dibutylbiguamide; dibenzylbiguamide;
diphenylbiguamide; ditolylbiguamide; dinaphthylbiguamide;
dicyclohexylbiguamide; dinorbornylbiguamide; diadamantylbiguamide;
ethylenedibiguamide; propylenedibiguamide;
tetramethylenedibiguamide; pentamethylenedibiguamide;
hexamethylenedibiguamide; heptamethylenedibiguamide;
octamethylenedibiguamide; phenylenedibiguamide;
piperazinedibiguamide; oxalyldibiguamide; malonyldibiguamide;
succinyldibiguamide; glutaryldibiguamide; adipyldibiguamide;
pimelyldibiguamide; suberyldibiguamide; phthalyldibiguamide;
paludrine; polyhexamethylene biguamide; 2-guanidinothiazole;
2-guanidinooxazole; 2-guanidinoimidazole; 3-guanidinopyrazole;
3-guanidino-1,2,4-triazole; 5-guanidinotetrazole; alexidine;
buformin; and moroxydine.
[0166] N Valence Stabilizer #20: Examples of diamidinomethanes,
bis(diamidinomethanes), and poly(diamidinomethanes) (N--N
bidentates, N--N tridentates, N--N tetradentates, and N--N
hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diamidinomethane; N-methyldiamidinomethane;
N-ethyldiamidinomethane; N-isopropyldiamidinomethane;
N-butyldiamidinomethane; N-benzyldiamidinomethane;
N-phenyldiamidinomethane; N-tolyldiamidinomethane;
N-naphthyldiamidinomethane; N-cyclohexyldiamidinomethane;
N-norbornyldiamidinomethane; N-adamantyldiamidinomethane;
dimethyldiamidinomethane; diethyldiamidinometbane;
diisopropyldiamidinomethane; dibutyldiamidinomethane;
dibenzyldiamidinomethane; diphenyldiamidinomethane;
ditolyldiamidinomethane; dinaphthyldiamidinomethane;
dicyclohexyldiamidinomethane; dinorbornyldiamidinomethane;
diadamantyldiamidinomethane; ethylenebisdiamidinomethane;
propylenebisdiamidinomethane; tetramethylenebisdiamidinomethane;
pentamethylenebisdiamidinomethane;
hexamethylenebisdiamidinomethane;
heptamethylenebisdiamidinomethane;
octamethylenebisdiamidinomethane; phenylenebisdiamidinomethane;
piperazinebisdiamidinomethane; oxalylbisdiamidinomethane;
malonylbisdiamidinomethane; succinylbisdiamidinomethane;
glutarylbisdiamidinomethane; phthalylbisdiamidinomethane;
2-ainidinomethylthiazole; 2-amidinomethyloxazole;
2-amidinomethylimidazol- e; 3-amidinomethylpyrazole;
3-amidinomethyl-1,2,4-triazole; and 5-amidinomethyltetrazole.
[0167] N Valence Stabilizer #21: Examples of imidoylguanidines,
amidinoguanidines, bis(imidoylguanidines), bis(amidinoguanidines),
poly(imidoylguanidines), and poly(amidinoguanidines) (N--N
bidentates, N--N tridentates, N--N tetradentates, and N--N
hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: acetimidoylguanidine; amidinoguanidine,
benzimidoylguanidine; cyclohexylimidoylguanidine;
pentafluorobenzimidoylguanidine; 2-N-imidoylaminothiazole;
2-N-imidoylaminooxazole; 2-N-imidoylaminoimidazole;
3-N-imidoylaminopyrazole; 3-N-imidoylamino-1,2,4-triazole; and
5-N-imidoylaminotetrazole.
[0168] N Valence Stabilizer #22: Examples of diformamidine oxides
(dicarbonimidic diamides), tricarbonimidic diamides,
tetracarbonimidic diamides, bis(diformamidine oxides), and
poly(diformamidine oxides) (N--N bidentates, N--N tridentates, or
N--N tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: diformamidine oxide; methyldiformamidine
oxide; ethyldiformamidine oxide; isopropyldiformamidine oxide;
butyldiformamidine oxide; benzyldiformamidine oxide;
phenyldiformamidine oxide; tolyldiformamidine oxide;
naphthyldiformamidine oxide; cyclohexyldiformamidine oxide;
norbornyldiformamidine oxide; adamantyldiformamidine oxide;
dimethyldiformamidine oxide; diethyldiformamidine oxide;
diisopropyldiformamidine oxide; dibutyldiformamidine oxide;
dibenzyldiformamidine oxide; diphenyldiformamidine oxide;
ditolyldiformamidine oxide; dinaphthyldiformamidine oxide;
dicyclohexyldiformamidine oxide; dinorbornyldiformamidine oxide;
diadamantyldiformamidine oxide; 2-O-amidinohydroxythiazole;
2-O-amidinohydroxyoxazole; 2-O-amidinohydroxyimidazole;
3-O-amidinohydroxypyrazole; 3-O-amidinohydroxy-1,2,4-triazole; and
5-O-amidinohydroxytetrazole.
[0169] N Valence Stabilizer #23: Examples of diformamidine sulfides
(thiodicarbonimidic diamides), thiotricarbonimidic diamides,
thiotetracarbonimidic diamides, bis(diformamidine sulfides), and
poly(diformamidine sulfides) (N--N bidentates, N--N tridentates, or
N--N tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: diformamidine sulfide; methyldiformamidine
sulfide; ethyldiformamidine sulfide; isopropyldiformamidine
sulfide; butyldiformamidine sulfide; benzyldiformamidine sulfide;
phenyldiformamidine sulfide; tolyldiformamidine sulfide;
naphthyldiformamidine sulfide; cyclohexyldiformamidine sulfide;
norbornyldiformamidine sulfide; adamantyldiformamidine sulfide;
dimethyldiformamidine sulfide; diethyldiformamidine sulfide;
diisopropyldiformamidine sulfide; dibutyldiformamidine sulfide;
dibenzyldiformamidine sulfide; diphenyldiformamidine sulfide;
ditolyldiformamidine sulfide; dinaphthyldiformamidine sulfide;
dicyclohexyldiformamidine sulfide; dinorbornyldiformamidine
sulfide; diadamantyldiformamidine sulfide;
phenylthiobisformamidine; 2-S-amidinomercaptothiazole;
2-S-amidinomercaptooxazole; 2-S-amidinomercaptoimidazole;
3-S-amidinomercaptopyrazole; 3-S-amidinomercapto-1,2,4-triazole;
and 5-S-amidinomercaptotetrazole.
[0170] N Valence Stabilizer #24: Examples of imidodicarbonimidic
acids, diimidodicarbonimidic acids, imidotricarbonimidic acids,
imidotetracarbonimidic acids, and derivatives thereof (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: imidodicarbonimidic acid, diimidodicarbonimidic
acid, imidotricarbonimidic acid, imidotetracarbonimidic acid;
O-methylimidodicarbonimidic acid; O-ethylimidodicarbonimidic acid;
O-isopropylimidodicarbonimidic acid; O-phenylimidodicarbonimidic
acid; O-benzylimidodicarbonimidic acid;
O-cyclohexylimidodicarbonimidic acid; O-naphthylimidodicarbonimidic
acid; O-norbornylimidodicarbonimidic acid;
O-adamantylimidodicarbonimidic acid;
O,O'-dimethylimidodicarbonimidic acid;
O,O'-diethylimidodicarbonimidic acid;
O,O'-diisopropylimidodicarbonimidic acid;
O,O'-diphenylimidodicarbo- nimidic acid;
O,O'-dibenzylimidodicarbonimidic acid;
O,O'-dicyclohexylimidodicarbonimidic acid;
O,O'-dinaphthylimidodicarbonim- idic acid;
O,O'-dinorbornylimidodicarbonimidic acid; and
O,O'-diadamantylimidodicarbonimidic acid.
[0171] N Valence Stabilizer #25: Examples of
thioimidodicarbonimidic acids, thiodiimidodicarbonimidic acids,
thioimidotricarbonimidic acids, thioimidotetracarbonimidic acids,
and derivatives thereof (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: thioimidodicarbonimidic
acid, thiodiimidodicarbonimidic acid, thioimidotricarbonimidic
acid, thioimidotetracarbonimidic acid;
O-methylthioimidodicarbonimidic acid;
O-ethylthioimidodicarbonimidic acid;
O-isopropylthioimidodicarbonimidic acid;
O-phenylthioimidodicarboni- midic acid;
O-benzylthioimidodicarbonimidic acid; O-cyclohexylthioimidodic-
arbonimidic acid; O-naphthylthioimidodicarbonimidic acid;
O-norbornylthioimidodicarbonimidic acid;
O-adamantylthioimidodicarbonimid- ic acid;
O,O'-dimethylthioimidodicarbonimidic acid;
O,O'-diethylthioimidodicarbonimidic acid;
O,O'-diisopropylthioimidodicarb- onimidic acid;
O,O'-diphenylthioimidodicarbonimidic acid;
O,O'-dibenzylthioimidodicarbonimidic acid;
O,O'-dicyclohexylthioimidodica- rbonimidic acid;
O,O'-dinaphthylthioimidodicarbonimidic acid;
O,O'-dinorbornylthioimidodicarbonimidic acid; and
O,O'-diadamantylthioimi- dodicarbonimidic acid.
[0172] N Valence Stabilizer #26: Examples of diimidoylimines,
diimidoylhydrazides, bis(diimidoylimines),
bis(diimidoylhydrazides), poly(diimidoylimines), and
poly(diimidoylhydrazides) (N--N Tridentates and N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diacetimidoylimine; dibenzimidoylimine; and
dicyclohexylimidoylimine.
[0173] N Valence Stabilizer #27: Examples of imidosulfamides,
diimidosulfamides, bis(imidosulfamides), bis(diimidosulfamides),
poly(imidosulfamides), and poly(diimidosulfamides) (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: imidosulfamidic acid, diimidosulfamidic acid;
O-phenylimidosulfamide; O-benzylimidosulfamide;
N-phenylimidosulfamide; N-benzylimidosulfamide;
O-phenyldiimidosulfamide; O-benzyldiimidosulfamide;
N-phenyldiimidosulfamide; and N-benzyldiimidosulfamide.
[0174] N Valence Stabilizer #28: Examples of phosphoramidimidic
triamides, bis(phosphoramidimidic triamides), and
poly(phosphoramidimidic triamides) and derivatives thereof (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphoramidimidic triamide;
N-phenylphosphoramidimidic triamide; N-benzylphosphoramidimidic
triamide; N-naphthylphosphoramidimidic triamide;
N-cyclohexylphosphoramidimidic triamide;
N-norbornylphosphoramidimidic triamide; N,N'-diphenylphosphorai-
nidimidic triamide; N,N'-dibenzylphosphoramidimidic triamide;
N,N'-dinaphthylphosphoramidimidic triamide;
N,N'-dicyclohexylphosphoramid- imidic triamide; and
N,N'-dinorbornylphosphoramidimidic triamide.
[0175] N Valence Stabilizer #29: Examples of phosphoramidimidic
acid, phosphorodiamidimidic acid, bis(phosphoramidimidic acid),
bis(phosphorodiamidimidic acid), poly(phosphoramidimidic acid),
poly(phosphorodiamidimidic acid), and derivatives thereof (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphoramidimidic acid, phosphorodiamidimidic
acid, O-phenylphosphoramidimidic acid; O-benzylphosphoramidimidic
acid; O-naphthylphosphoramidimidic acid;
O-cyclohexylphosphoramidimidic acid; O-norbornylphosphorainidimidic
acid; O,O'-diphenylphosphoramidimidic acid;
O,O'-dibenzylphosphoramidimidic acid;
O,O'-dinaphthylphosphoramidim- idic acid;
O,O'-dicyclohexylphosphoramidimidic acid; and
O,O'-dinorbornylphosphoramidimidic acid.
[0176] N Valence Stabilizer #30: Examples of
phosphoramidimidodithioic acid, phosphorodiamidimidothioic acid,
bis(phosphoramidimidodithioic acid), bis(phosphorodiamidimidothioic
acid), poly(phospboramidimidodithio- ic acid),
poly(phosphorodiamidimidothioic acid), and derivatives thereof
(N--N Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphoramidimidodithioic acid,
phosphorodiamidimidothioic acid, S-phenylphosphoramidimidodithioic
acid; S-benzylphosphoramidimidodithoic acid;
S-naphthylphosphoramidimidodithioic acid;
S-cyclohexylphosphoramidi- midodithioic acid;
S-norbornylphosphoramidimidodithioic acid;
S,S'-diphenylphosphoramidimidodithioic acid;
S,S'-dibenzylphosphoramidimi- dodithioic acid;
S,S'-dinaphthylphosphoramidimidodithioic acid;
S,S'-dicyclohexylphosphoramidimidodithioic acid; and
S,S'-dinorbornylphosphoramidimidodithioic acid.
[0177] N Valence Stabilizer #31: Examples of azo compounds with
amino, imino, oximo, diazeno, or hydrazido substitution at the
ortho- (for aryl) or alpha- or beta- (for alkyl) positions,
bis[o-(H.sub.2N--) or alpha- or beta-(H.sub.2N--)azo compounds], or
poly[o-(H.sub.2N--) or alpha- or beta-(H.sub.2N--)azo compounds)
(N--N Bidentates, N--N Tridentates, N--N Tetradentates, or N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: o-aminoazobenzene; o,o'-diaminoazobenzene;
(2-pyridine)azobenzene; 1-phenylazo-2-naphthylami- ne;
pyridineazo-2-naphthol (PAN); pyridineazoresorcinol (PAR);
o-hydroxy-o'-(beta-aminoethylamino)azobenzene; Benzopurpurin 4B;
Congo Red; Fat Brown RR; benzopurpurin; Congo Red; Direct Red 75;
Mordant Brown 48; Nitro Red; 2-imidazolylazobenzene;
2-benzimidazolylazobenzene; 3-pyrazolylazobenzene;
3-(1,2,4-triazolyl)azobenzene; 2-pyridylazobenzene;
2-pyrazinylazobenzene; and 2-pyrimidinylazobenzene.
[0178] N Valence Stabilizer #32: Examples of diazeneformimidamides
(diazeneamidines), diazeneacetimidamides
(diazene-alpha-amidinoalkanes(al- kenes)),
bis(diazeneformimidamides), bis(diazeneacetimidamides),
poly(diazeneformimidamides), and poly(diazeneacetimidamides) (N--N
Bidentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazeneformimidamide (diazeneamidine); diazeneacetimidamide
(diazene-alpha-amidinomethane); phenyldiazeneformimidamide;
triphenyldiazeneformimidamide; phenyldiazeneacetimidamide; and
triphenyldiazeneacetimidamide.
[0179] N Valence Stabilizer #33: Examples of diazeneformimidic
acid, diazeneacetimidic acid, bis(diazeneformimidic acid),
bis(diazeneacetimidic acid), poly(diazeneformimidic acid),
poly(diazeneacetimidic acid), and derivatives thereof (N--N
Bidentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazeneformimidic acid, diazeneacetimidic acid,
phenyldiazeneformimidic acid, diphenyldiazeneformimidic acid,
phenyldiazeneacetimidic acid, and diphenyldiazeneacetimidic
acid.
[0180] N Valence Stabilizer #34: Examples of diazeneformimidothioic
acid, diazeneacetimidothioic acid, bis(diazeneformimidothioic
acid), bis(diazeneacetimidothioic acid),
poly(diazeneformimidothioic acid), poly(diazeneacetimidothioic
acid), and derivatives thereof (N--N Bidentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diazeneformimidothioic
acid, diazeneacetimidothioic acid, phenyldiazeneformimidothioic
acid, diphenyldiazeneformimidothioic acid,
phenyldiazeneacetimidothioic acid, and
diphenyldiazeneacetimidothioic acid.
[0181] N Valence Stabilizer #35: Examples of imidoyldiazenes,
bis(imidoyldiazenes), and poly(imidoyldiazenes), (N--N Tridentates
and N--N Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: acetimidoyldiazene; benzimidoyldiazene; and
cyclohexylimidoyldiazene.
[0182] N Valence Stabilizer #36: Examples of
diazenediformimidamides (1,2-diazenediamidines),
diazenediacetimidamides (1,2-diazene-di-alpha-am-
idinoalkanes(alkenes)), bis(diazenediformimidamides),
bis(diazenediacetimidamides), poly(diazenediformimidamides), and
poly(diazenediacetimidamides) (N--N Tridentates and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diazenediformimidamide (1,2-diazenediamidine),
diazenediacetimidamide (1,2-diazene-di-alpha-amidinomethane);
diphenyldiazenediformimidamide; tetraphenyldiazenediformimidamide;
diphenyldiazenediacetimidamide; and
tetraphenyldiazenediacetimidamide.
[0183] N Valence Stabilizer #37: Examples of diazenediformimidic
acid, diazenediacetimidic acid, bis(diazenediformimidic acid),
bis(diazenediacetimidic acid), poly(diazenediformimidic acid), and
poly(diazenediacetimidic acid), and derivatives thereof (N--N
Tridentates and N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diazenediformimidic
acid, diazenediacetimidic acid, diphenyldiazenediformimidic acid,
and diphenyldiazenediacetimidic acid.
[0184] N Valence Stabilizer #38: Examples of
diazenediformimidothioic acid, diazenediacetimidothioic acid,
bis(diazenediformimidothioic acid), bis(diazenediacetimidothioic
acid), poly(diazenediformimidothioic acid), and
poly(diazenediacetimidothioic acid), and derivatives thereof (N--N
Tridentates and N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diazenediformimidothioic
acid, diazenediacetimidothioic acid,
diphenyldiazenediformimidothioic acid, and
diphenyldiazenediacetimidothioic acid.
[0185] N Valence Stabilizer #39: Examples of diimidoyldiazenes,
bis(diimidoyldiazenes), and poly(diimidoyldiazenes), (N--N
Tridentates and N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diacetimidoyldiazene;
dibenzimidoyldiazene; and dicyclohexylimidoyldiazene.
[0186] N Valence Stabilizer #40: Examples of ortho-amino (or
-hydrazido) substituted formazans, bis(o-amino or -hydrazido
substituted formazans), and poly(o-amino or -hydrazido substituted
formazans) (N--N Bidentates, N--N Tridentates, N--N Tetradentates,
and N--N Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 1-(2-aminophenyl)-3,5-d- iphenylformazan;
and 1,5-bis(2-aminophenyl)-3-phenylformazan.
[0187] N Valence Stabilizer #41: Examples of ortho-amino (or
-hydrazido) substituted azines (including ketazines), bis(o-amino
or hydrazido substituted azines), and poly(o-amino or hydrazido
substituted azines) (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-amino-1-benzalazine;
2-amino-1-naphthalazine; and 2-amino-1-cyclohexanonazine.
[0188] N Valence Stabilizer #42: Examples of Schiff Bases with one
Imine (C.dbd.N) Group and with ortho- or alpha- or beta-amino or
imino or oximo or diazeno or hydrazido substitution (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, N--N
Pentadentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: N-(2-Aminobenzaldehydo)-
isopropylamine; N-(2-Pyridinecarboxaldehydo)isopropylamine;
N-(2-Pyrrolecarboxaldehydo)isopropylamine;
N-(2-Acetylpyridino)isopropyla- mine;
N-(2-Acetylpyrrolo)isopropylamine;
N-(2-Aminoacetophenono)isopropyla- mine;
N-(2-Aminobenzaldehydo)cyclohexylamine;
N-(2-Pyridinecarboxaldehydo)- cyclohexylamine;
N-(2-Pyrrolecarboxaldehydo)cyclohexylamine;
N-(2-Acetylpyridino)cyclohexylamine;
N-(2-Acetylpyrrolo)cyclohexylamine;
N-(2-Aminoacetophenono)cyclohexylamine;
N-(2-Aminobenzaldehydo)aniline;
N-(2-Pyridinecarboxaldehydo)aniline;
N-(2-Pyrrolecarboxaldehydo)aniline; N-(2-Acetylpyridino)aniline;
N-(2-Acetylpyrrolo)aniline; N-(2-Aminoacetophenono)aniline;
N-(2-Aminobenzaldehydo)aminonorbornane;
N-(2-Pyridinecarboxaldehydo)aminonorbornane;
N-(2-Pyrrolecarboxaldehydo)a- minonorbornane;
N-(2-Acetylpyridino)aminonorbornane;
N-(2-Acetylpyrrolo)aminonorbornane;
N-(2-Aminoacetophenono)aminonorbornan- e; 2-pyrrolecarboxaldehyde
phenylhydrazone; 2-pyrrolecarboxaldehyde 2-pyridyl hydrazone;
2-aminobenzaldehyde phenylhydrazone (nitrin); and
2-aminobenzaldehyde 2-pyridyl hydrazone. Also includes hydrazones
with ortho-N substitution.
[0189] N Valence Stabilizer #43: Examples of Schiff Bases with two
Imine (C.dbd.N) Groups and without ortho- (for aryl constituents)
or alpha- or beta- (for alkyl constituents) hydroxy, carboxy,
carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo,
diazeno, or hydrazido substitution (N--N Bidentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N'-(Glyoxalo)diisopropylamine; N,N'-(Glyoxalo)dicyclohexylamine;
N,N'-(Glyoxalo)dianiline; N,N'-(Glyoxalo)di-aminonorbornane;
N,N'-(Malondialdehydo)diisopropylamine- ;
N,N'-(Malondialdehydo)dicyclohexylamine;
N,N'-(Malondialdehydo)dianiline- ;
N,N'-(Malondialdehydo)di-aminonorbornane;
N,N'-(Phthalicdialdehydo)diiso- propylamine;
N,N'-(Phthalicdialdehydo)dicyclohexylamine;
N,N'-(Phthalicdialdehydo)dianiline;
N,N'-(Phthalicdialdehydo)di-aminonorb- ornane;
N,N'-(Formylcamphoro)diisopropylamine; N,N'-(Formylcamphoro)dicycl-
ohexylamine; N,N'-(Formylcamphoro)dianiline;
N,N'-(Formylcamphoro)di-amino- norbornane;
N,N'-(Acetylacetonato)diisopropylamine;
N,N'-(Acetylacetonato)dicyclohexylamine;
N,N'-(Acetylacetonato)dianiline; N,N'-(Acetyl
acetonato)di-aminonorbornane; N,N'-(Diacetylbenzeno)diisopro-
pylamine; N,N'-(Diacetylbenzeno)dicyclohexylamine;
N,N'-(Diacetylbenzeno)d- ianiline;
N,N'-(Diacetylbenzeno)di-aminonorbornane;
N,N'-(1,2-Cyclohexanono)diisopropylamine;
N,N'-(1,2-Cyclohexanono)dicyclo- hexylamine;
N,N'-(1,2-Cyclohexanono)dianiline; N,N'-(1,2-Cyclohexanono)di--
aminonorbornane; N,N'-(Camphorquinono)diisopropylamine;
N,N'-(Camphorquinono)dicyclohexylamine;
N,N'-(Camphorquinono)dianiline;
N,N'-(Camphorquinono)di-aminonorbornane;
N,N'-(Benzaldehydo)ethylenediami- ne;
N,N'-(Naphthaldehydo)ethylenediamine;
N,N'-(Acetophenono)ethylenediami- ne;
N,N'-(Benzaldehydo)trimethylenediamine;
N,N'-(Naphthaldehydo)trimethyl- enediamine;
N,N'-(Acetophenono)trimethylenediamine;
N,N'-(Benzaldehydo)cyclohexane-1,2-diamine;
N,N'-(Naphthaldehydo)cyclohex- ane-1,2-diamine;
N,N'-(Acetophenono)cyclohexane-1,2-diamine;
N,N'-(Benzaldehydo)-1,2-diaminobenzene;
N,N'-(Naphthaldehydo)-1,2-diamino- benzene;
N,N'-(Acetophenono)-1,2-diaminobenzene; N,N'-(Acetylacetonato)eth-
ylenediamine; N,N'-(Acetylacetonato)-1,2-cyclohexylenediamine;
N,N'-(Acetylacetonato)-1,2-propylenediamine;
N,N'-(Glyoxalo)-o-phenylened- iamine; and
N,N'-(Glyoxalo)ethylenediamine. Also includes dihydrazones.
[0190] N Valence Stabilizer #44: Examples of Schiff Bases with two
Imine (C.dbd.N) Groups and with ortho- or alpha- or beta-amino or
imino or oximo or diazeno or hydrazido substitution (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, N--N
Pentadentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
N,N'-(2,6-Pyridinedicarboxaldehydo)diisopropylamine;
N,N'-(2,6-Pyridinedicarboxaldehydo)dicyclohexylamine;
N,N'-(2,6-Pyridinedicarboxaldehydo)dianiline;
N,N'-(2,6-Pyridinedicarboxa- ldehydo)di-aminonorbornane;
N,N'-(2,5-Pyrroledicarboxaldehydo)diisopropyla- mine;
N,N'-(2,5-Pyrroledicarboxaldehydo)dicyclohexylamine;
N,N'-(2,5-Pyrroledicarboxaldehydo)dianiline;
N,N'-(2,5-Pyrroledicarboxald- ehydo)di-aminonorbornane;
N,N'-(o-Aminophthalicdialdehydo)diisopropylamine- ;
N,N'-(o-Aminophthalicdialdehydo)dicyclohexylamine;
N,N'-(o-Aminophthalicdialdehydo)dianiline;
N,N'-(o-Aminophthalicdialdehyd- o)di-aminonorbornane;
N,N'-(o-Aminoformylcamphoro)diisopropylamine;
N,N'-(o-Aminoformylcamphoro)dicyclohexylamine;
N,N'-(o-Aminoformylcamphor- o)dianiline;
N,N'-(o-Aminoformylcamphoro)di-aminonorbornane;
N,N'-(2,6-Diacetylpyridino)diisopropylamine;
N,N'-(2,6-Diacetylpyridino)d- icyclohexylamine;
N,N'-(2,6-Diacetylpyridino)dianiline;
N,N'-(2,6-Diacetylpyridino)di-aminonorbornane;
N,N'-(o-Aminodiacetylbenze- no)diisopropylamine;
N,N'-(o-Aminodiacetylbenzeno)dicyclohexylamine;
N,N'-(o-Aminodiacetylbenzeno)dianiline;
N,N'-(o-Aminodiacetylbenzeno)di-a- minonorbornane;
N,N'-(3,6-Diamino-1,2-cyclohexanono)diisopropylamine;
N,N'-(3,6-Diamino-1,2-cyclohexanono)dicyclohexylamine;
N,N'-(3,6-Diamino-1,2-cyclohexanono)dianiline;
N,N'-(3,6-Diamino-1,2-cycl- ohexanono)di-aminonorbornane;
N,N'-(2,5-Diacetylpyrrolo)diisopropylamine;
N,N'-(2,5-Diacetylpyrrolo)dicyclohexylamine;
N,N'-(2,5-Diacetylpyrrolo)di- aniline;
N,N'-(2,5-Diacetylpyrrolo)di-aminonorbornane;
N,N'-(o-Aminobenzaldehydo)ethylenediamine;
N,N'-(o-Aminonaphthaldehydo)et- hylenediamine;
N,N'-(o-Aminoacetophenono)ethylenediamine;
N,N'-(o-Aminobenzaldehydo)trimethylenediamine;
N,N'-(o-Aminonaphthaldehyd- o)trimethylenediamine;
N,N'-(o-Aminoacetophenono)trimethylenediamine;
N,N'-(o-Aminobenzaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Aminonaphthaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Aminoacetophenono)cyclohexane-1,2-diamine;
N,N'-(o-Aminobenzaldehydo)-1,2-diaminobenzene;
N,N'-(o-Aminonaphthaldehyd- o)-1,2-diaminobenzene; and
N,N'-(o-Aminoacetophenono)-1,2-diaminobenzene. Also includes
hydrazones with ortho-N substitution.
[0191] N Valence Stabilizer #45: Examples of Schiff Bases with
three Imine (C--N) Groups and without ortho- (for aryl
constituents) or alpha- or beta- (for alkyl constituents) hydroxy,
carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino,
oximo, diazeno, or hydrazido substitution (N--N Tridentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N',N"-(Benzaldehydo)tris(2-aminoethyl)amine;
N,N',N"-(Naphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N"-(Acetophenono)tris(2-aminoethyl)amine. Also includes
trihydrazones.
[0192] N Valence Stabilizer #46: Examples of Schiff Bases with
three Imine (C.dbd.N) Groups and with ortho- or alpha- or
beta-amino or imino or oximo or diazeno or hydrazido substitution
(N--N Tridentates, N--N Tetradentates, N--N Pentadentates, or N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: N,N',N"-(o-Aminobenzald-
ehydo)tris(2-aminoethyl)amine;
N,N',N"-(o-Aminonaphthaldehydo)tris(2-amino- ethyl)amine; and
N,N',N"-(o-Aminoacetophenono)tris(2-aminoethyl)amine.
[0193] S Valence Stabilizer #1: Examples of macrocyclic,
macrobicyclic, and macropolycyclic oligothioketones (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of thioketones (especially in the beta
position) (S--S Bidentates, S--S Tetradentates, and S--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hexathioketocyclotetracosane
([24]ane(.dbd.S).sub.6); hexathioketocycloheneicosane
([21]ane(.dbd.S).sub.6); hexathioketocyclooctadecane
([18]ane(.dbd.S).sub.6); hexathioketocyclopentadecane
([15]ane(S).sub.6); tetrathioketocycloeicosane
([20]ane(.dbd.S).sub.4); tetrathioketocyclooctadecane
([18]ane(.dbd.S).sub.4); tetrathioketocyclohexadecane
([16]ane(.dbd.S).sub.4); tetrathioketocyclotetradecane
([14]ane(S).sub.4); tetrathioketocyclododec- ane
([12]ane(.dbd.S).sub.4); dithioketocyclohexadecane
([16]ane(.dbd.S).sub.2); dithioketocyclotetraadecane
([14]ane(.dbd.S).sub.2); dithioketocyclododecane
([12]ane(.dbd.S).sub.2); dithioketocyclodecane ([1]ane(S).sub.2);
and dithioketocyclooctane ([8]ane(.dbd.S).sub.2).
[0194] S Valence Stabilizer #2: Examples of macrocyclic,
macrobicyclic, and macropolycyclic dithiolenes (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of alpha-, alpha-dithiolenes (meaning
two thiol groups on a single carbon atom in the ring) (S--S
Bidentates, S--S Tetradentates, and S--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexathiolocyclotetracosane ([24]ane(--SH).sub.6);
hexathiolocycloheneicosane ([21]ane(--SH).sub.6);
hexathiolocyclooctadeca- ne ([18]ane(--SH).sub.6);
hexathiolocyclopentadecane ([15]ane(--SH).sub.6);
tetrathiolocycloeicosane ([20]ane(--SH).sub.4);
tetrathiolocyclooctadecane ([18]ane(--SH).sub.4);
tetrathiolocyclohexadec- ane ([16]ane(--SH).sub.4);
tetrathiolocyclotetradecane ([14]ane(--SH).sub.4);
tetrathiolocyclododecane ([12]ane(--SH).sub.4);
dithiolocyclohexadecane ([16]ane(--SH).sub.2);
dithiolocyclotetraadecane ([14]ane(--SH).sub.2);
dithiolocyclododecane ([12]ane(--SH).sub.2); dithiolocyclodecane
([11]ane(--SH).sub.2); and dithiolocyclooctane
([8]ane(--SH).sub.2).
[0195] S Valence Stabilizer #3: Examples of dithioimidodialdehydes,
dithiohydrazidodialdehydes (thioacyl thiohydrazides),
bis(dithioimidodialdehydes), bis(dithiohydrazidodialdehydes),
poly(ditbioimidodialdehydes), and poly(dithiohydrazidodialdehydes)
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithiodiacetamide, dithiodipropanamide, dithiodibutanamide,
dithiodibenzamide, and dithiodicyclohexamide.
[0196] S Valence Stabilizer #4: Examples of dithioimidodicarbonic
acids, dithiohydrazidodicarbonic acids, bis(dithioimidodicarbonic
acids), bis(dithiohydrazidodicarbonic acids),
poly(dithioimidodicarbonic acids), poly(dithiohydrazidodicarbonic
acids) and derivatives thereof (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithioimidodicarbonic acid,
dithiohydrazidodicarbonic acid, O-pbenyldithioimidodicarbonic acid,
O-benzyldithioimidodicarbonic acid,
O-cyclohexyldithioimidodicarbonic acid,
O-norbornyldithioimidodicarbonic acid,
O,O'-diphenyldithioimidodica- rbonic acid,
O,O'-dibenzyldithioimidodicarbonic acid,
O,O'-dicyclohexyldithioimidodicarbonic acid, and
O,O'-norbornyldithioimid- odicarbonic acid.
[0197] S Valence Stabilizer #5: Examples of 1,3-dithioketones
(dithio-beta-ketonates), 1,3,5-trithioketones,
bis(1,3-dithioketones), and poly(1,3-dithioketones) (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexafluoropentanedithione; 1,3-diphenyl-1,3-propanedithione;
thiobenzoylthiopinacolone; dithiocyclohexoylmethane;
diphenylpentanetrithionate; tetramethylnonanetrithionate;
bexafluoroheptanetrithionate; trifluoroheptanetrithionate;
1-(2-thienyl)-1,3-butanedithione,
1-(2-naphthyl)-1,3-butanedithione, trifluorothioacetylthiocampbor;
and 1,3-indandithione.
[0198] S Valence Stabilizer #6: Examples of 1,2-dithioketones
(dithiolenes, dithio-alpha-ketonates), 1,2,3-trithioketones,
dithiotropolonates, o-dithioquinones, bis(1,2-dithioketones), and
poly(1,2-dithioketones) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiotropolone; 1,2-dithiobenzoquinone
(o-dithioquinone)(o-benzenedi- thiolate)(bdt);
di-tert-butyl-1,2-dithiobenzoquinone;
hexafluoro-1,2-dithiobenzoquinone; 1,2-ditbionaphthoquinone;
9,10-dithiophenanthroquinone; ethylenedithiolene (edt);
maleonitriledithiolene (mnt); trifluoromethyldithiolene (tfd);
carbomethoxydithiolene (cmt); trithionedithiolene (dmit);
toluenedithiolate (tdt); dithiomanaldehyde
(propenethionethiolate)(ptt); dithioacetylacetonate (SacSac);
dijulolidinedithiolene; 2,3-piperazinedithiolate;
di(4-aminophenyl)dithiolene; dimercaptoisotrithione (dmit);
(4-octylphenyl)dithiolene; benzenetetrathiol; tetrathiosquaric
acid; trithiodeltic acid; pentathiocroconic acid; dithiocroconic
acid; hexathiorhodizonic acid; dithiorhodizonic acid;
ethylenetetrathiol; trans-butadienetetrathiolate; tetrathiooxalic
acid; 1,2-indandithione; naphthothioquinone;
acenapthenethioquinone; aceanthrenethioquinone; and
indole-2,3-dithione (thioisatin).
[0199] S Valence Stabilizer #7: Examples of dithiomalonamides
(dithiomalonodiamides), bis(dithiomalonamides), and
polydithiomalonamides (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiomalonamide, N-phenyldithiomalonamide,
N-benzyldithiomalonamide, N-pentafluorophenyldithiomalonamide,
N-cyclohexyldithiomalonamide, N-norbornyldithiomalonamide,
N,N'-diphenyldithiomalonamide, N,N'-dibenzyldithiomalonamide,
N,N'-dipentafluorophenyldithiomalonamide,
N,N'-dicyclohexyldithiomalonamide, and
N,N'-norbornyldithiomalonamide.
[0200] S Valence Stabilizer #8: Examples of
2-thioacylthioacetamides, bis(2-thioacylthioacetamides), and
poly(2-thioacylthioacetamides) (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 2-thioacetothioacetamid- e,
N-phenyl-2-thioacetothioacetamide,
N-pentafluorophenyl-2-thioacetothioa- cetamide,
N-benzyl-2-thioacetothioacetamide, N-cyclohexyl-2-thioacetothioa-
cetamide, N-norbornyl-2-thioacetothioacetamide,
N-phenyl-2-thiobenzothioac- etamide,
N-pentafluorophenyl-2-pentafluorothiobenzothioacetamide, and
N-cyclohexyl-2-thiocyclohexothioacetamide.
[0201] S Valence Stabilizer #9: Examples of dithioacyl sulfides,
bis(dithioacyl sulfides), and poly(dithioacyl sulfides), (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithioacetyl sulfide; dithiopropanoyl sulfide; dithiobenzoyl
sulfide; and dithiopentafluorobenzoyl sulfide.
[0202] S Valence Stabilizer #10: Examples of trithiodicarbonic
diamides, bis(trithiodicarbonic diamides), and
poly(trithiodicarbonic diamides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: trithiodicarbonic diamide;
N-phenyltrithiodicarbonic diamide; N-pentafluorophenyltrithiodic-
arbonic diamide; N-benzyltrithiodicarbonic diamide;
N-cyclohexyltrithiodicarbonic diamide; N-norbornyltrithiodicarbonic
diamide; N,N'-diphenyltrithiodicarbonic diamide;
N,N'-dipentafluorophenyl- trithiodicarbonic diamide;
N,N'-dibenzyltrithiodicarbonic diamide;
N,N'-dicyclohexyltrithiodicarbonic diamide; and
N,N'-dinorbornyltrithiodi- carbonic diamide.
[0203] S Valence Stabilizer #11: Examples of pentathio-,
tetrathio-, or trithiodicarbonic acids, bis(pentathio-, tetrathio-,
or trithiodicarbonic acids), poly(pentathio-, tetrathio-, or
trithiodicarbonic acids), and derivatives thereof (S--S Bidentates,
S--S Tridentates, S--S Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: pentathiodicarbonic
acid, tetrathiodicarbonic acid, trithiodicarbonic acid,
O-phenyltrithiodicarbonic acid, O-benzyltrithiodicarbonic acid,
O-cyclohexyltrithiodicarbonic acid, O-norbornyltrithiodicarbonic
acid, O,O'-diphenyltrithiodicarbonic acid,
O,O'-dibenzyltrithiodicarbonic acid,
O,O'-dicyclohexyltrithiodicarbonic acid, and
O,O'-dinorbornyltrithiodicar- bonic acid.
[0204] S Valence Stabilizer #12: Examples of dithiohypophosphoric
acids, bis(dithiohypophosphoric acids), poly(dithiohypophosphoric
acids), and derivatives thereof (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiohypophosphoric acid,
methyldithiohypophosphoric acid, isopropyldithiohypophosphoric
acid, tert-butyldithiohypophosphoric acid,
phenyldithiohypophosphoric acid,
pentafluorophenyldithiohypophosphoric acid,
benzyldithiohypophosphoric acid, cyclohexyldithiohypophosphoric
acid, norbornyldithiohypophosphoric acid,
dimethyldithiohypophosphoric acid, diisopropyldiothiohypophosphoric
acid, di-tert-butyldithiohypophosp- horic acid,
diphenyldithiohypophosphoric acid, dipentafluorophenyldithiohy-
pophosphoric acid, dibenzyldithiohypophosphoric acid,
dicyclohexyldithiohypophosphoric acid, and
dinorbornyldithiohypophosphori- c acid.
[0205] S Valence Stabilizer #13: Examples of
dithiohypophosphoramides, bis(dithiohypophosphoramides), and
poly(dithiohypophosphoramides) (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiohypophosphoramide- ,
N-methyldithiohypophosphoramide,
N-isopropyldithiohypophosphoramide,
N-tert-butyldithiohypophosphoramide,
N-phenyldithiohypophosphoramide,
N-pentafluorophenyldithiohypophosphoramide,
N-benzyldithiohypophosphorami- de,
N-cyclohexyldithiohypophosphoramide,
N-norbornyldithiohypophosphoramid- e,
N,N'"-dimethyldithiohypophosphoramide,
N,N'"-diisopropyldithiohypophosp- horamide,
N,N'"-di-tert-butyldithiohypophosphoramide,
N,N'"-diphenyldithiohypophosphoramide,
N,N'"-di-pentafluorophenyldithiohy- pophosphoramide,
N,N'"-dibenzyldithiohypophosphoramide,
N,N'"-dicyclohexyldithiohypophosphoramide, and
N,N'"-dinorbornyldithiohyp- ophosphoramide.
[0206] S Valence Stabilizer #14: Examples of
dithioimidodiphosphoric acids, dithiohydrazidodiphosphoric acids,
bis(dithioimidodiphosphoric acids), bis(dithiohydrazidodiphosphoric
acids), poly(dithioimidodiphospho- ric acids),
poly(dithiohydrazidodiphosphoric acids), and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithioimidodiphosphoric acid, methyldithioimidodiphosphoric acid,
isopropyldithioimidodiphosphori- c acid,
tert-butyldithioimidodiphosphoric acid, phenyldithioimidodiphospho-
ric acid, pentafluorophenyldithioimidodiphosphoric acid,
benzyldithioimidodiphosphoric acid,
cyclohexyldithioimidodiphosphoric acid,
norbornyldithioimidodiphosphoric acid,
dimethyldithioimidodiphospho- ric acid,
diisopropyldiothioimidodiphosphoric acid,
di-tert-butyldithioimidodiphosphoric acid,
diphenyldithioimidodiphosphori- c acid,
di-pentafluorophenyldithioimidodiphosphoric acid,
dibenzyldithioimidodiphosphoric acid,
dicyclohexyldithioimidodiphosphoric acid, and
dinorbornyldithioimidodiphosphoric acid.
[0207] S Valence Stabilizer #15: Examples of
dithioimidodiphosphoramides, dithiohydrazidodiphosphoramides,
bis(dithioimidodiphosphoramides),
bis(dithiohydrazidodiphosphoramides),
poly(dithioimidodiphosphoramides), and
poly(dithiohydrazidodiphosphoramides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: dithioimidodiphosphoramide,
N-methyldithioimidodiphosphoramide,
N-isopropyldithioimidodiphosphoramide- ,
N-tert-butyldithioimidodiphosphoramide,
N-phenyldithioimidodiphosphorami- de,
N-pentafluorophenyldithioimidodiphosphoramide,
N-benzyldithioimidodiph- osphoramide,
N-cyclohexyldithioimidodiphosphoramide,
N-norbornyldithioimidodiphosphoramide,
N,N'"-dimethyldithioimidodiphospho- ramide,
N,N'"-diisopropyldithioimidodiphosphoramide,
N,N'"-di-tert-butyldithioimidodiphosphoramide,
N,N'"-diphenyldithioimidod- iphosphoramide,
N,N'"-di-pentafluorophenyldithioimidodiphosphoramide,
N,N'"-dibenzyldithioimidodiphosphoramide,
N,N'"-dicyclohexyldithioimidodi- phosphoramide, and
N,N'"-dinorbornyldithioimidodiphosphoramide.
[0208] S Valence Stabilizer #16: Examples of
dithiodiphosphoramides, bis(dithiodiphosphoramides), and
poly(dithiodiphosphoramides) (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiodiphosphoramide,
N-methyldithiodiphosphoramide, N-isopropyldithiodiphosphoramide,
N-tert-butyldithiodiphosphoramide, N-phenyldithiodiphosphoramide,
N-pentafluorophenyldithiodiphosphoramide,
N-benzyldithiodiphosphoramide, N-cyclohexyldithiodiphosphoramide,
N-norbornyldithiodiphosphoramide,
N,N'"-dimethyldithiodiphosphoramide,
N,N'"-diisopropyldithiodiphosphorami- de,
N,N'"-di-tert-butyldithiodiphosphoramide,
N,N'"-diphenyldithiodiphosph- oramide,
N,N'"-di-pentafluorophenyldithiodiphosphoramide,
N,N'"-dibenzyldithiodiphospboramide,
N,N'"-dicyclohexyldithiodiphosphoram- ide, and
N,N'"-dinorbornyldithiodiphosphoramide.
[0209] S Valence Stabilizer #17: Examples of dithiodiphosphoric
acids, bis(dithiodiphosphoric acids), poly(dithiodiphosphoric
acids), and derivatives thereof (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiodiphosphoric acid,
methyldithiodiphosphoric acid, isopropyldithiodiphosphoric acid,
tert-butyldithiodiphosphoric acid, phenyldithiodiphosphoric acid,
pentafluorophenyldithiodiphosphoric acid, benzyldithiodiphosphoric
acid, cyclohexyldithiodiphosphoric acid,
norbornyldithiodiphosphoric acid, dimethyldithiodiphosphoric acid,
diisopropyldiothiodiphosphoric acid,
di-tert-butyldithiodiphosphoric acid, diphenyldithiodiphosphoric
acid, di-pentafluorophenyldithiodiphosph- oric acid,
dibenzyldithiodiphosphoric acid, dicyclohexyldithiodiphosphoric
acid, and dinorbornyldithiodiphosphoric acid.
[0210] S Valence Stabilizer #18: Examples of trithiophosphoric
acids (phosphorotritbioic acids), bis(trithiophosphoric acids),
poly(trithiophosphoric acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trithiophosphoric acid, O-phenyltrithiophosphoric acid,
O-benzyltrithiophosphoric acid, O-cyclohexyltrithiophosphoric acid,
O-norbornyltrithiophosphoric acid, O,S-diphenyltrithiophosphoric
acid, O,S-dibenzyltrithiophosphoric acid,
O,S-dicyclohexyltrithiophosphoric acid, and
O,S-dinorbornyltrithiophospho- ric acid.
[0211] S Valence Stabilizer #19: Examples of dithiophosphoric acids
(phosphorodithioic acids), bis(dithiophosphoric acids),
poly(dithiophosphoric acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithiophosphoric acid, O-phenyldithiophosphoric acid,
O-benzyldithiophosphoric acid, O-cyclohexyldithiophosphoric acid,
O-norbornyldithiophosphoric acid, O,O-diphenyldithiophosphoric
acid, O,O-dibenzyldithiophosphoric acid,
O,O-dicyclohexyldithiophosphoric acid, and
O,O-dinorbornyldithiophosphori- c acid.
[0212] S Valence Stabilizer #20: Examples of tetrathiophosphoric
acids (phosphorotetrathioic acids), bis(tetrathiophosphoric acids),
poly(tetrathiophosphoric acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetrathiophosphoric acid, S-phenyltetrathiophosphoric acid,
S-benzyltetrathiophosphoric acid, S-cyclohexyltetrathiophosphoric
acid, S-norbornyltetrathiophosphoric acid,
S,S-diphenyltetrathiophosphoric acid,
S,S-dibenzyltetrathiophosphor- ic acid,
S,S-dicyclohexyltetrathiophosphoric acid, and
S,S-dinorbornyltetrathiophosphoric acid.
[0213] S Valence Stabilizer #21: Examples of
phosphoro(dithioperoxo)dithio- ic acids,
bis[phosphoro(dithioperoxo)dithioic acids],
poly[phosphoro(dithioperoxo)dithioic acids], and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+ include, but are not
limited to: phosphoro(dithioperoxo)d- ithioic acid,
O-phenylphosphoro(dithioperoxo)dithioic acid,
O-benzylphosphoro(dithioperoxo)dithioic acid,
O-cyclohexylphosphoro(dithi- operoxo)dithioic acid,
O-norbornylphosphoro(dithioperoxo)dithioic acid,
O,S-diphenylphosphoro(dithioperoxo)dithioic acid,
O,S-dibenzylphosphoro(d- ithioperoxo)ditbioic acid,
O,S-dicyclohexylphosphoro(dithioperoxo)dithioic acid, and
O,S-dinorbornylphosphoro(dithioperoxo)dithioic acid.
[0214] S Valence Stabilizer #22: Examples of
phosphoro(dithioperoxo)thioic acids,
bis[phosphoro(dithioperoxo)thioic acids], poly[phosphoro(dithioper-
oxo)thioic acids], and derivatives thereof (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: phosphoro(dithioperoxo)thioic
acid, O-phenylphosphoro(dithioperoxo)thioic acid,
O-benzylphosphoro(dithioperox- o)thioic acid,
O-cyclohexylphosphoro(dithioperoxo)thioic acid,
O-norbornylphosphoro(ditbioperoxo)thioic acid,
O,S-diphenylphosphoro(dith- ioperoxo)thioic acid,
O,S-dibenzylphosphoro(dithioperoxo)thioic acid,
O,S-dicyclohexylphosphoro(dithioperoxo)thioic acid, and
O,S-dinorbornylphosphoro(dithioperoxo)thioic acid.
[0215] S Valence Stabilizer #23: Examples of
phosphoro(dithioperoxo)trithi- oic acids,
bis[phosphoro(dithioperoxo)trithioic acids],
poly[phosphoro(dithioperoxo)trithioic acids], and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: phosphoro(dithioperoxo)- trithioic acid,
O-phenylphosphoro(dithioperoxo)trithioic acid,
O-benzylphosphoro(dithioperoxo)trithioic acid,
O-cyclohexylphosphoro(dith- ioperoxo)trithioic acid,
O-norbornylphosphoro(dithioperoxo)trithioic acid,
O,S-diphenylphosphoro(dithioperoxo)trithioic acid,
O,S-dibenzylphosphoro(dithioperoxo)trithioic acid,
O,S-dicyclohexylphosphoro(dithioperoxo)trithioic acid, and
O,S-dinorbornylphosphoro(dithioperoxo)trithioic acid.
[0216] S Valence Stabilizer #24: Examples of
beta-mercaptothioketones, beta-mercaptothioaldehydes,
bis(beta-mercaptothioketones), bis(beta-mercaptothioaldehydes),
poly(beta-mercaptothioketones), and
poly(beta-mercaptothioaldehydes) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: 4-mercaptopentan-2-thione;
1,3-diphenyl-3-mercaptopropanethioaldehyde- ;
1,3-dibenzyl-3-mercaptopropanethioaldehyde;
1,3-dicyclohexyl-3-mercaptop- ropanethioaldehyde;
1,3-dinorbornyl-3-mercaptopropanethioaldehyde;
1,3-di(2-thienyl)-3-mercaptopropanethioaldehyde;
1,3-di(2-furyl)-3-mercap- topropanethioaldehyde;
o-mercaptothioacetophenone; 5-mercapto-1,4-dithiona- phthoquinone;
1-mercaptothioacridone; 1-mercaptodithioanthraquinone;
1,8-dimercaptodithioanthraquinone; and
beta-mercaptothiobenzophenone.
[0217] S Valence Stabilizer #25: Examples of
N-(aminomethylthiol)thioureas [N-(aminomercaptomethyl)thioureas],
bis[N-(aminomethylthiol)thioureas], and
poly[N-(aminomethylthiol)thioureas] (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: N'-(aminomercaptomethyl)thiourea;
N,N"-dimethyl-N'-(aminomercaptomethyl)thiourea;
N,N'-diethyl-N'-(aminomer- captomethyl)thiourea;
N,N"-isopropyl-N'-(aminomercaptomethyl)thiourea;
N,N"-diphenyl-N'-(aminomercaptomethyl)thiourea;
N,N"-dibenzyl-N'-(aminone- rcaptomethyl)thiourea;
N,N"-dicyclohexyl-N'-(aminomercaptomethyl)thiourea; and
N,N"-dinorbornyl-N'-(aminomercaptomethyl)thiourea.
[0218] S Valence Stabilizer #26: Examples of dithiooxamides,
bis(dithiooxamides), and poly(dithiooxamides) (S--S Bidentates,
S--S Tridentates, S--S Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: dithiooxamide (rubeanic
acid), N-methyldithiooxamide; N-ethyldithiooxamide;
N-isopropyldithiooxamide; N-phenyldithiooxamide;
N-benzyldithiooxamide; N-cyclohexyldithiooxamide;
N-norbornyldithiooxamide; N,N'-dimethyldithiooxamide;
N,N'-diethyldithiooxamide; N,N'-diisopropyldithiooxamide;
N,N'-diphenylditbiooxamide; N,N'-dibenzyldithiooxamide;
N,N'-dicyclohexyldithiooxamide; and
N,N'-dinorbornyldithiooxamide.
[0219] S Valence Stabilizer #27: Examples of 1,1-dithiolates,
bis(1,1-dithiolates), and poly(1,1-dithiolates) (S--S Bidentates
and S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 1,1-dicyano-2,2-ethylene dithiolate
(i-mnt); 1,1-dicarboalkoxy-2,2-et- hylene dithiolate (DED);
1,1-di(trifluoromethyl)-2,2-ethylenedithiolate;
1,1-di(pentafluorophenyl)-2,2-ethylenedithiolate;
1-pentamethylene-2,2-et- hylene dithiolate; and 1-nitroethylene
dithiolate.
[0220] S Valence Stabilizer #28: Examples of dithiomonocarboxylic
acids, tri- and tetrathiodicarboxylic Acids,
bis(dithiomonocarboxylic acids), bis(tri- and tetrathiodicarboxylic
acids), poly(dithiomonocarboxylic acids), poly(tri- and
tetrathiodicarboxylic acids), and derivatives thereof (S--S
Bidentates and S--S Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: dithioacetic acid;
dithiopropionic acid; dithiobenzoic acid (dtb); dithiophenylacetic
acid (dtpa); dithiocyclohexanoic acid; dithiofuroic acid;
dithionaphthoic acid; phenyl dithioacetate; phenyl
dithiopropionate; phenyl dithiobenzoate; phenyl
dithiocyclohexanoate; phenyl dithiofuroate; phenyl
dithionaphthoate; tetrathiooxalic acid; tetrathiomalonic acid;
tetrathiosuccinic acid; trithiooxalic acid; trithiomalonic acid;
trithiosuccinic acid; diphenyl tetrathiooxalate; diphenyl
tetrathiomalonate; diphenyl tetrathiosuccinate; diphenyl
trithiooxalate; diphenyl trithiomalonate; diphenyl
trithiosuccinate; pyridine dithiocarboxylic acid; pyrrole
dithiocarboxylic acid; thiophene dithiocarboxylic acid;
dithionaphthoic acid; and tetrathiocamphonic acid.
[0221] S Valence Stabilizer #29: Examples of perthiomonocarboxylic
acids, perthiodicarboxylic acids, bis(perthiomonocarboxylic acids),
bis(perthiodicarboxylic acids), poly(perthiomonocarboxylic acids),
poly(perthiodicarboxylic acids), and derivatives thereof (S--S
Bidentates and S--S Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: perthioacetic acid;
perthiopropionic acid; perthiobenzoic acid; perthiophenylacetic
acid; perthiocyclohexanoic acid; perthiofuroic acid;
perthionaphthoic acid; phenyl perthioacetate; phenyl
perthiopropionate; phenyl perthiobenzoate; phenyl
perthiocyclohexanoate; phenyl perthiofuroate; phenyl
perthionaphthoate; perthiooxalic acid; perthiomalonic acid;
perthiosuccinic acid; diphenyl perthiooxalate; diphenyl
perthiomalonate; diphenyl perthiosuccinate; dithiole-3-thione
(dithione-3-thione); and benzodithiole-3-thione
(benzodithione-3-thione).
[0222] S Valence Stabilizer #30: Examples of dithiocarbonates,
trithiocarbonates, perthiocarbonates, bis(dithiocarbonates),
bis(trithiocarbonates), and bis(perthiocarbonates) (S--S Bidentates
and S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: S,S-diethyldithiocarbonate;
S,S-diisopropyldithiocarbonate; S,S-diphenyldithiocarbonate;
S,S-dibenzyldithiocarbonate; S,S-dicyclohexyldithiocarbonate;
S,S-dinorbornyldithiocarbonate; diethyltrithiocarbonate;
diisopropyltrithiocarbonate; diphenyltrithiocarbonate;
dibenzyltrithiocarbonate; dicyclohexyltrithiocarbonate; and
dinorbornyltrithiocarbonate.
[0223] S Valence Stabilizer #31: Examples of dithiocarbamates,
bis(dithiocarbamates), and poly(dithiocarbamates) (including
N-hydroxydithiocarbamates and N-mercaptodithiocarbamates) (S--S
Bidentates, S--S Tridentates, and S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dimethyldithiocarbamate (dmdtc);
di(trifluorodimethyl)dithiocarbamate; diethyldithiocarbamate
(dedtc); dipropyldithiocarbamate; diisopropyldithiocarbamate;
dibutyldithiocarbamate; ditertbutyldithiocarbamate;
dicyanamidodithiocarbamate; azidothioformates;
diphenyldithiocarbamate; di(pentafluorophenyl)dithiocarbamate;
dibenzyldithiocarbamate; dinaphthyldithiocarbamate;
dicyclohexyldithiocarbamate; dinorbornyldithiocarbamate;
diadamantyldithiocarbamate; pyrrolidinodithiocarbamate (pyrdtc);
piperidinodithiocarbamate (pipdtc); morpholinodithiocarbamate
(mordtc); thiamorpholinodithiocarbamate;
3-pyrrolinodithiocarbamate; pyrrolodithiocarbamate;
oxazolodithiocarbamate; isoxazolodithiocarbamate;
thiazolodithiocarbamate- ; isothiazolodithiocarbamate;
indolodithiocarbamate; carbazolodithiocarbamate;
pyrazolinodithiocarbamate; imidazolinodithiocarbamate;
pyrazolodithiocarbamate; imidazolodithiocarbamate;
indazolodithiocarbamate; and triazolodithiocarbamate.
[0224] S Valence Stabilizer #32: Examples of dithiocarbazates
(dithiocarbazides), bis(dithiocarbazates), and
poly(dithiocarbazates) (S--S Bidentates, S--S Tridentates, and S--S
Tetradentates; or possibly N--S Bidentates, N--S Tridentates, and
N--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: N,N'-dimethyldithiocarb- azate;
N,N'-di(trifluoromethyl)dithiocarbazate;
N,N'-diethyldithiocarbazat- e; N,N'-diphenyldithiocarbazate;
N,N'-dibenzyldithiocarbazate;
N,N'-di(pentafluorophenyl)dithiocarbazate;
N,N'-dicyclohexyldithiocarbaza- te; and
N,N'-dinorbornyldithiocarbazate.
[0225] S Valence Stabilizer #33: Examples of thiocyanate ligands (S
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn include, but are not
limited to: thiocyanate (--SCN).
[0226] O Valence Stabilizer #1: Examples of biurets
(imidodicarbonic diamides), isobiurets, biureas, triurets,
triureas, bis(biurets), bis(isobiurets), bis(biureas),
poly(biurets), poly(isobiurets), and poly(biureas) (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to: biuret,
isobiuret, biurea, triuret, triurea, nitrobiuret, dinitrobiuret,
aminobiuret, diaminobiuret, oxybiuret, dioxybiuret, cyanobiuret,
methylbiuret, ethylbiuret, isopropylbiuret, phenylbiuret,
benzylbiuret, cyclohexylbiuret, norbornylbiuret, adamantylbiuret,
dimethylbiuret, diethylbiuret, diisopropylbiuret, diphenylbiuret,
dibenzylbiuret, dicyclohexylbiuret, dinorbornylbiuret, and
diadamantylbiuret.
[0227] O Valence Stabilizer #2: Examples of acylureas, aroylureas,
bis(acylureas), bis(aroylureas), poly(acylureas), and
poly(aroylureas) (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: formylurea, acetylurea, benzoylurea,
cyclohexoylurea, pentafluorobenzoylurea, N-methylacetylurea,
N-phenylbenzoylurea, and N-cyclohexylcyclohexoylurea.
[0228] O Valence Stabilizer #3: Examples of imidodialdehydes,
hydrazidodialdehydes (acyl hydrazides), bis(imidodialdehydes),
bis(hydrazidodialdehydes), poly(imidodialdehydes), and
poly(hydrazidodialdehydes) (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diacetamide, dipropanamide, dibutanamide,
dibenzamide, and dicyclohexamide.
[0229] O Valence Stabilizer #4: Examples of imidodicarbonic acids,
hydrazidodicarbonic acids, bis(imidodicarbonic acids),
bis(hydrazidodicarbonic acids), poly(imidodicarbonic acids),
poly(hydrazidodicarbonic acids) and derivatives thereof (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
imidodicarbonic acid, hydrazidodicarbonic acid,
O-phenylimidodicarbonic acid, O-benzylimidodicarbonic acid,
O-cyclohexylimidodicarbonic acid, o-norbornylimidodicarbonic acid,
O,O'-diphenylimidodicarbonic acid, O,O'-dibenzylimidodicarbonic
acid, O,O'-dicyclohexylimidodicarbonic acid, and
O,O'-dinorbornylimidodicarbonic acid.
[0230] O Valence Stabilizer #5: Examples of imidodisulfamic acid,
imidodisulfuric acid, bis(imidodisulfamic acid),
bis(imidodisulfuric acid), poly(imidodisulfamic acid), and
poly(imidodisulfuric acid) and derivatives thereof (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
imidodisulfamic acid, imidodisulfuric acid, N-phenylimidodisulfamic
acid, N-benzylimidodisulfamic acid, N-cyclohexylimidodisulfamic
acid, N-norbornylimidodisulfamic acid, N,N'-diphenylimidodisulfamic
acid, N,N'-dibenzylimidodisulfainic acid,
N,N'-dicyclohexylimidodisulfamic acid, and
N,N'-norbornylimidodisulfamic acid.
[0231] O Valence Stabilizer #6: Examples of 1,3-diketones
(beta-diketonates), 1,3,5-triketones, bis(1,3-diketones), and
poly(1,3-diketones), all with a molecular weight greater than 125
(O--O Bidentates, O--O Tridentates, O--O Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexafluoropentanedione; dibenzoylmethane
(1,3-diphenyl-1,3-propanedione); benzoylpinacolone;
dicyclohexoylmethane; diphenylpentanetrionate; dibenzoylacetone;
benzoylacetylacetone; dibenzoylacetylacetone;
tetramethylnonanetrionate; hexafluoroheptanetrionate;
trifluoroheptanetrionate; trifluoroacetylcamphor (facam); and
1,3-indandione.
[0232] O Valence Stabilizer #7: Examples of 1,2-diketones
(alpha-diketonates), 1,2,3-triketones, tropolonates, o-quinones,
bis(1,2-diketones), and poly(1,2-diketones), all with a molecular
weight greater than 100 (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tropolone; 1,2-benzoquinone (o-quinone);
di-tert-butyl-1,2-benzoquinone; hexafluoro-1,2-benzoquinone;
1,2-naphthoquinone; 9,10-phenanthroquinone; and 1,2-indandione.
[0233] O Valence Stabilizer #8: Examples of malonamides
(malonodiamides), bis(malonamides), and polymalonamides (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
malonamide, N-phenylmalonamide, N-benzylmalonamide,
N-pentafluorophenylmalonamide, N-cyclohexylmalonamide,
N-norbornylmalonamide, N,N'-diphenylmalonainide,
N,N'-dibenzylnalonamide, N,N'-dipentafluorophenylmalonamide,
N,N'-dicyclohexylmalonamide, and N,N'-norbornylmalonamide.
[0234] O Valence Stabilizer #9: Examples of 2-acylacetamides,
bis(2-acylacetamides), and poly(2-acylacetamides) (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-acetoacetamide,
N-phenyl-2-acetoacetamide, N-pentafluorophenyl-2-acetoacetamide,
N-benzyl-2-acetoacetamide, N-cyclohexyl-2-acetoacetamide,
N-norbornyl-2-acetoacetamide, N-phenyl-2-benzoacetamide,
N-pentafluorophenyl-2-pentafluorobenzoacetamid- e, and
N-cyclohexyl-2-cyclohexoacetamide.
[0235] O Valence Stabilizer #10: Examples of monothiodicarbonic
diamides, bis(monothiodicarbonic diamides), and
poly(monothiodicarbonic diamides) (O--O Bidentates, O--O
Tridentates, O--O Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: monothiodicarbonic diamide;
N-phenylmonothiodicarbonic diamide; N-pentafluorophenylmonothiod-
icarbonic diamide; N-benzylmonothiodicarbonic diamide;
N-cyclohexylmonothiodicarbonic diamide;
N-norbornylmonothiodicarbonic diamide;
N,N'-diphenylmonothiodicarbonic diamide; N,N'-dipentafluoropheny-
lmonothiodicarbonic diamide; N,N'-dibenzylmonothiodicarbonic
diamide; N,N'-dicyclohexylmonothiodicarbonic diamide; and
N,N'-dinorbornylmonothio- dicarbonic diamide.
[0236] O Valence Stabilizer #11: Examples of monothiodicarbonic
acids, bis(monothiodicarbonic acids), poly(monothiodicarbonic
acids), and derivatives thereof (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: monothiodicarbonic acid,
O-phenylmonothiodicarbonic acid, O-benzylmonothiodicarbonic acid,
O-cyclohexylmonothiodicarbonic acid, O-norbornylmonothiodicarbonic
acid, O,O'-diphenylmonothiodicarbonic acid,
O,O'-dibenzylmonothiodicarbonic acid,
O,O'-dicyclohexylmonothiodicarbonic acid, and
O,O'-dinorbornylmonothiodicarbonic acid.
[0237] O Valence Stabilizer #12: Examples of trithionic acid,
bis(trithionic acid), poly(trithionic acid), and derivatives
thereof (O--O Bidentates, O--O Tridentates, O--O Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diphenyl trithionate, dipentafluorodiphenyl
trithionate, dicyclohexyl trithionate, and dinorbornyl
trithionate.
[0238] O Valence Stabilizer #13: Examples of hypophosphoric acids,
bis(hypophosphoric acids), and poly(hypophosphoric acids), and
derivatives thereof (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hypophosphoric acid, O-methylhypophosphoric acid,
O-isopropylhypophosphoric acid, O-tert-butylhypophosphoric acid,
O-phenylhypophosphoric acid, O-pentafluorophenylhypophosphoric
acid, O-benzylhypophosphoric acid, O-cyclohexylhypophosphoric acid,
O-norbornylhypophosphoric acid, O,O"-dimethylhypophosphoric acid,
O,O"-diisopropylhypophosphoric acid,
O,O"-di-tert-butylhypophosphoric acid, O,O"-diphenylhypophosphoric
acid, O,O"-di-pentafluorophenylhypophos- phoric acid,
O,O"-dibenzylhypophosphoric acid, O,O"-dicyclohexylhypophosph- oric
acid, and O,O"-dinorbornylhypophosphoric acid.
[0239] O Valence Stabilizer #14: Examples of hypophosphoramides,
bis(hypophosphoramides), and poly(hypophosphoramides) (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hypophosphoramide, N-methylhypophosphoramide,
N-isopropylhypophosphoramide, N-tert-butylhypophosphoramide,
N-phenylhypophosphoramide, N-pentafluorophenylhypophosphoramide,
N-benzylhypophosphoramide, N-cyclohexylhypophosphoramide,
N-norbornylhypophosphoramide, N,N'"-dimethylhypophosphoramide,
N,N'"-diisopropylhypophosphoramide,
N,N'"-di-tert-butylhypophosphoramide,
N,N'"-diphenylhypophosphoramide,
N,N'"-di-pentafluorophenylhypophosphoramide,
N,N'"-dibenzylhypophosphoram- ide,
N,N'"-dicyclohexylhypophosphoramide, and
N,N'"-dinorbornylhypophospho- ramide.
[0240] O Valence Stabilizer #15: Examples of imidodiphosphoric
acids, hydrazidodiphosphoric acids, bis(imidodiphosphoric acids),
bis(hydrazidodiphosphoric acids), poly(imidodiphosphoric acids),
poly(hydrazidodiphosphoric acids), and derivatives thereof (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
imidodiphosphoric acid, methylimidodiphosphoric acid,
isopropylimidodiphosphoric acid, tert-butylimidodiphosphoric acid,
phenylimidodiphosphoric acid, pentafluorophenylimidodiphosphoric
acid, benzylimidodiphosphoric acid, cyclohexylimidodiphosphoric
acid, norbornylimidodiphosphoric acid, dimethylimidodiphosphoric
acid, diisopropylimidodiphosphoric acid,
di-tert-butylimidodiphosphoric acid, diphenylimidodiphosphoric
acid, di-pentafluorophenylimidodiphosphoric acid,
dibenzylimidodiphosphoric acid, dicyclohexylimidodiphosphoric acid,
and dinorbornylimidodiphosphori- c acid.
[0241] O Valence Stabilizer #16: Examples of imidodiphosphoramides,
hydrazidodiphosphoramides, bis(imidodiphosphoramides),
bis(hydrazidodiphosphoramides), poly(imidodiphosphoramides), and
poly(hydrazidodiphosphoramides) (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: imidodiphosphoramide,
N-methylimidodiphosphoramide, N-isopropylimidodiphosphoramide,
N-tert-butylimidodiphosphoramide, N-phenylimidodiphosphoramide,
N-pentafluorophenylimidodiphosphoramide,
N-benzylimidodiphosphoramide, N-cyclohexylimidodiphosphoramide,
N-norbornylimidodiphosphoramide,
N,N'"-dimethylimidodiphosphoramide,
N,N'"-diisopropylimidodiphosphoramide,
N,N'"-di-tert-butylimidodiphosphor- amide,
N,N'"-diphenylimidodiphosphoramide,
N,N'"-di-pentafluorophenylimido- diphosphoramide,
N,N'"-dibenzylimidodiphosphoramide,
N,N'"-dicyclohexylimidodiphosphoramide, and
N,N'"-dinorbornylimidodipbosp- horamide.
[0242] O Valence Stabilizer #17: Examples of diphosphoramides,
bis(diphosphoramides), and poly(diphospboramides) (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diphosphoramide,
N-methyldphosphoramide, N-isopropyldiphosphoramide,
N-tert-butyldiphosphoramide, N-phenyldiphosphoramide,
N-pentafluorophenyldiphosphoramide, N-benzyldiphosphoramide,
N-cyclohexyldiphosphoramide, N-norbornyldiphosphoramide,
N,N'"-dimethyldiphosphoramide, N,N'"-diisopropyldiphosphoramide,
N,N'"-di-tert-butyldiphosphoramide, N,N'"-diphenyldiphosphoramide,
N,N'"-di-pentafluorophenyldiphosphoramide,
N,N'"-dibenzyldiphosphoramide, N,N'"-dicyclohexyldiphosphoramide,
and N,N'"-dinorbornyldiphosphoramide.
[0243] O Valence Stabilizer #18: Examples of beta-hydroxyketones,
beta-hydroxyaldehydes, bis(beta-hydroxyketones),
bis(beta-hydroxyaldehyde- s), poly(beta-hydroxyketones), and
poly(beta-hydroxyaldehydes) (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+ include,
but are not limited to: 4-hydroxypentan-2-one;
1,3-diphenyl-3-hydroxypropanal; 1,3-dibenzyl-3-hydroxypropanal;
1,3-dicyclohexyl-3-hydroxypropanal;
1,3-dinorbornyl-3-hydroxypropanal;
1,3-di(2-thienyl)-3-hydroxypropanal;
1,3-di(2-furyl)-3-hydroxypropanal; o-hydroxyacetophenone; juglone;
alizarin; 1-hydroxyanthraquinone; 1,8-hydroxyanthraquinone;
1-hydroxyacridone; and beta-hydroxybenzophenone- .
[0244] O Valence Stabilizer #19: Examples of N-(aminomethylol)ureas
[N-(aminohydroxymethyl)ureas], bis[N-(aminomethylol)ureas], and
poly[N-(aminomethylol)ureas] (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: N'-(aminohydroxymethyl)urea;
N,N"-dimethyl-N'-(aminohydroxymethyl)ure- a;
N,N'-diethyl-N'-(aminohydroxymethyl)urea;
N,N"-isopropyl-N'-(aminohydro- xymethyl)urea;
N,N"-diphenyl-N'-(aminohydroxymethyl)urea;
N,N"-dibenzyl-N'-(aminohydroxymethyl)urea;
N,N"-dicyclohexyl-N'-(aminohyd- roxymethyl)urea; and
N,N"-dinorbornyl-N'-(aminohydroxymethyl)urea.
[0245] O Valence Stabilizer #20: Examples of oxamides,
bis(oxamides), and poly(oxamides) (O--O Bidentates, O--O
Tridentates, O--O Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: oxamide, N-methyloxamide;
N-ethyloxamide; N-isopropyloxamide; N-phenyloxamide;
N-benzyloxamide; N-cyclohexyloxamide; N-norbornyloxamide;
N,N'-dimethyloxamide; N,N'-diethyloxamide; N,N'-diisopropyloxamide;
N,N'-diphenyloxamide; N,N'-dibenzyloxamide;
N,N'-dicyclohexyloxamide; and N,N'-dinorbornyloxamide.
[0246] O Valence Stabilizer #21: Examples of squaric acids and
derivatives thereof (O--O Bidentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: deltic acid; squaric
acid; croconic acid; and rhodizonic acid.
[0247] O Valence Stabilizer #22: Examples of dicarboxylic acids,
bis(dicarboxylic acids), poly(dicarboxylic acids), and derivatives
thereof (O--O Bidentates and O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to: oxalic
acid; malonic acid; succinic acid; diphenyl oxalate; diphenyl
malonate; and diphenyl succinate.
[0248] O Valence Stabilizer #23: Examples of carbamates,
bis(carbamates), and poly(carbamates) (including
N-hydroxycarbamates and N-mercaptocarbamates) (O--O Bidentates,
O--O Tridentates, and O--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dimethylcarbamate (dmc); di(trifluorodimethyl)carbamate; ethyl
carbamate; diethylcarbamate (dec); dipropylcarbamate;
diisopropylcarbamate; dibutylcarbamate; ditertbutylcarbamate;
dicyanamidocarbamate; diphenylcarbainate;
di(pentafluorophenyl)carbamate; dibenzylcarbamate;
dinaphthylcaibamate; dicyclohexylcarbamate; dinorbornylcarbamate;
diadamantylcarbamate; pyrrolidinocarbamate (pyrc);
piperidinocarbamate (pipc); morpholinocarbamate (morc);
thiamorpholinocarbamate; 3-pyrrolinocarbamate; pyrrolocarbamate;
oxazolocarbamate; isoxazolocarbamate; thiazolocarbamate;
isothiazolocarbamate; indolocarbamate; carbazolocarbamate;
pyrazolinocarbamate; imidazolinocarbamate; pyrazolocarbamate;
imidazolocarbamate; indazolocarbamate; and triazolocarbamate.
[0249] O Valence Stabilizer #24: Examples of carbimates,
bis(carbimates), and poly(carbimates) (O--O Bidentates, O--O
Tridentates, and O--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: methylcarbimate;
trifluoromethylcarbimate; ethylcarbimate; propylcarbimate;
isopropylcarbimate; butylcarbimate; tertbutylcarbimate;
cyanocarbimate; cyanamidocarbimate; azidocarbimate;
phenylcarbimate; pentafluorophenylcarbimate; benzylcarbimate;
naphthylcarbimate; cyclohexylcarbimate; norbornylcarbimate; and
adamantylcarbimate. [Note: Carbimates tend to stabilize lower
oxidation states in metal ions.]
[0250] O Valence Stabilizer #25: Examples of cyanate ligands (O
monodentates) that meet the 5 requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: cyanate (--OCN).
[0251] N--S Valence Stabilizer #1: Examples of diformamidine
disulfides (thioperoxydicarbonimidic diamides),
thioperoxytricarbonimidic diamides, thioperoxytetracarbonimidic
diamides, bis(diformamidine disulfides), and poly(diformamidine
disulfides) (N--S bidentates, N--N--S tridentates, or N--S
tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diformamidine disulfide; methyldiformamidine
disulfide; ethyldiformamidine disulfide; isopropyldiformamidine
disulfide; butyldiformamidine disulfide; benzyldiformamidine
disulfide; phenyldiformamidine disulfide; tolyldiformamidine
disulfide; naphthyldiformamidine disulfide; cyclohexyldiformamidine
disulfide; norbornyldiformamidine disulfide; adamantyldiformamidine
disulfide; dimethyldiformamidine disulfide; diethyldiformamidine
disulfide; diisopropyldiformamidine disulfide; dibutyldiformamidine
disulfide; dibenzyldiformamidine disulfide; diphenyldiformamidine
disulfide; ditolyldiformamidine disulfide; dinaphthyldiformamidine
disulfide; dicyclohexyldiformamidine disulfide;
dinorbornyldiformamidine disulfide; diadamantyldiformamidine
disulfide; 2-S-amidinodisulfidothiazole;
2-S-amidinodisulfidooxazole; 2-S-amidinodisulfidoimidazole;
3-S-amidinodisulfidopyrazole; 3-S-amidinodisulfido-1,2,4-triazole;
and 5-S-amidinodisulfidotetrazole.
[0252] N--S Valence Stabilizer #2: Examples of
S-amidinodithiocarbamates, bis(S-amidinodithiocarbamates), and
poly(S-amidinodithiocarbamates) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: S-amidinodithiocarbamate; N-methyl-S-amidinodithi-
ocarbamate; N-ethyl-S-amidinodithiocarbamate;
N-isopropyl-S-amidinodithioc- arbamate;
N-butyl-S-amidinodithiocarbamate; N-benzyl-S-amidinodithiocarbam-
ate; N-phenyl-S-amidinodithiocarbamate;
N-tolyl-S-amidinodithiocarbamate;
N-naphthyl-S-amidinodithiocarbamate;
N-cyclohexyl-S-amidinodithiocarbamat- e;
N-norbornyl-S-amidinodithiocarbamate;
N-adamantyl-S-amidinodithiocarbam- ate;
N,N'-dimethyl-S-amidinodithiocarbamate;
N,N'-diethyl-S-amidinodithioc- arbamate;
N,N'-diisopropyl-S-amidinodithiocarbamate;
N,N'-dibutyl-S-amidinodithiocarbamate;
N,N'-dibenzyl-S-amidinodithiocarba- mate;
N,N'-diphenyl-S-amidinodithiocarbamate;
N,N'-ditolyl-S-amidinodithio- carbamate;
N,N'-dinapbthyl-S-amidinodithiocarbamate;
N,N'-dicyclohexyl-S-amidinodithiocarbamate;
N,N'-dinorbornyl-S-amidinodit- hiocarbamate;
N,N'-diadamantyl-S-amidinodithiocarbamate;
etbylenebis(S-amidinodithiocarbamate);
propylenebis(S-amidinodithiocarbam- ate);
phenylenebis(S-amidinodithiocarbamate);
piperazinebis(S-amidinodithi- ocarbamate);
oxalylbis(S-amidinodithiocarbamate); malonylbis(S-amidinodith-
iocarbamate); succinylbis(S-amidinodithiocarbamate);
phthalylbis(S-amidinodithiocarbamate); 2-S-dithiocarbamatothiazole;
2-S-dithiocarbamatooxazole; 2-S-dithiocarbamatoimidazole;
3-S-dithiocarbamatopyrazole; 3-S-dithiocarbamato-1,2,4-triazole;
and 5-S-dithiocarbamatotetrazole.
[0253] N--S Valence Stabilizer #3: Examples of
O-amidinothiocarbamates, bis(O-amidinothiocarbamates), and
poly(O-amidinothiocarbamates) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: O-amidinothiocarbamate; N-methyl-O-amidinothiocar-
bamate; N-ethyl-O-amidinothiocarbamate;
N-isopropyl-O-amidinothiocarbamate- ;
N-butyl-O-amidinothiocarbamate; N-benzyl-O-amidinothiocarbamate;
N-pbenyl-O-amidinothiocarbamate; N-tolyl-O-amidinothiocarbamate;
N-naphthyl-O-amidinothiocarbamate;
N-cyclohexyl-O-amidinothiocarbamate;
N-norbornyl-O-amidinothiocarbamate;
N-adamantyl-O-amidinothiocarbamate;
N,N'-dimethyl-O-amidinothiocarbamate;
N,N'-diethyl-O-amidinothiocarbamate- ;
N,N'-diisopropyl-O-amidinothiocarbamate;
N,N'-dibutyl-O-amdinothiocarbam- ate;
N,N'-dibenzyl-O-amidinothiocarbamate;
N,N'-diphenyl-O-amidinothiocarb- amate;
N,N'-ditolyl-O-amidinothiocarbamate;
N,N'-dinaphthyl-O-amidinothioc- arbamate; N,N'-di
cyclohexyl-O-amidinothiocarbamate;
N,N'-dinorbornyl-O-amidinothiocarbamate;
N,N'-diadamantyl-O-amidinothioca- rbamate;
ethylenebis(O-amidinothiocarbamate); propylenebis(O-amidinothioca-
rbamate); phenylenebis(O-amidinothiocarbamate);
piperazinebis(O-amidinothi- ocarbamate);
oxalylbis(O-amidinothiocarbamate); malonylbis(O-amidinothioca-
rbamate); succinylbis(O-amidinothiocarbamate);
phthalylbis(O-amidinothioca- rbamate);
2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole;
2-O-monothiocarbamatoimidazole; 3-O-monothiocarbamatopyrazole;
3-O-monothiocarbamato-1,2,4-triazole; and
5-O-monothiocarbamatotetrazole.
[0254] N--S Valence Stabilizer #4: Examples of
S-amidinoperoxythiocarbamat- es,
bis(S-amidinoperoxythiocarbamates), and
poly(S-amidinoperoxythiocarbam- ates) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: S-amidinoperoxythiocarbamate;
N-methyl-S-amidinoperoxythiocarbamate;
N-ethyl-S-amidinoperoxythiocarbama- te;
N-isopropyl-S-amidinoperoxythiocarbamate;
N-butyl-S-amidinoperoxythioc- arbamate;
N-benzyl-S-amidinoperoxythiocarbamate; N-phenyl-S-amidinoperoxyt-
hiocarbamate; N-tolyl-S-amidinoperoxythiocarbamate;
N-naphthyl-S-amidinoperoxythiocarbamate;
N-cyclohexyl-S-amidinoperoxythio- carbamate;
N-norbornyl-S-amidinoperoxythiocarbamate;
N-adamantyl-S-amidinoperoxythiocarbamate;
N,N'-dimethyl-S-amidinoperoxyth- iocarbamate;
N,N'-diethyl-S-amidinoperoxythiocarbamate;
N,N'-diisopropyl-S-amidinoperoxythiocarbamate;
N,N'-dibutyl-S-amidinopero- xythiocarbamate;
N,N'-dibenzyl-S-amidinoperoxythiocarbamate;
N,N'-diphenyl-S-amidinoperoxythiocarbamate;
N,N'-ditolyl-S-amidinoperoxyt- hiocarbamate;
N,N'-dinaphthyl-S-amidinoperoxythiocarbamate;
N,N'-dicyclohexyl-S-amidinoperoxythiocarbamate;
N,N'-dinorbornyl-S-amidin- operoxythiocarbamate;
N,N'-diadamantyl-S-amidinoperoxythiocarbamate;
ethylenebis(S-amidinoperoxythiocarbamate);
propylenebis(S-amidinoperoxyth- iocarbamate);
phenylenebis(S-amidinoperoxythiocarbamate);
piperazinebis(S-amidinoperoxythiocarbamate);
oxalylbis(S-amidinoperoxythi- ocarbamate);
malonylbis(S-amidinoperoxythiocarbamate);
succinylbis(S-amidinoperoxythiocarbamate); and
phthalylbis(S-amidinoperox- ythiocarbamate).
[0255] N--S Valence Stabilizer #5: Examples of phosphorimidothioic
acid; phosphorimidodithioic acid; phosphorimidotrithioic acid;
bis(phosphorimidothioic acid); bis(phosphorimidodithioic acid);
bis(phosphorimidotrithioic acid); poly(phosphorimidothioic acid);
poly(phosphorimidodithioic acid); poly(phosphorimidotrithioic
acid); and derivatives thereof (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphorimidothioic acid; phosphorimidodithioic
acid; phosphorimidotritbioic acid; O-phenylphosphorimidothioic
acid; O-benzylphosphorimidothioic acid;
O-cyclohexylphosphorimidothioic acid;
O-norbornylphosphorimidothioic acid;
O,O'-diphenylphosphorimidothioic acid;
O,O'-dibenzylphosphorimidoth- ioic acid;
O,O'-dicyclohexylphosphorimidothioic acid; and
O,O'-dinorbornylphosphorimidothioic acid.
[0256] N--S Valence Stabilizer #6: Examples of phosphorothioic
triamides, bis(phosphorothioic triamides), and poly(phosphorothioic
triamides) (N--S Bidentates and N--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphorothioic triamide; phosphorothioic trihydrazide;
phosphoramidothioic dihydrazide; N-phenylphosphorothioic triamide;
N-benzylphosphorothioic triamide; N-cyclohexylphosphorothioic
triamide; N-norbornylphosphorothioic triamide;
N,N'-diphenylphosphorothio- ic triamide;
N,N'-dibenzylphosphorothioic triamide;
N,N'-dicyclohexylphosphorothioic triamide; and
N,N'-dinorbornylphosphorot- hioic triamide.
[0257] N--S Valence Stabilizer #7: Examples of
phosphoramidotrithioic acid, phosphorodiamidodithioic acid,
bis(phosphoramidotritbioic acid), bis(phosphorodiamidodithioic
acid), poly(phosphoramidotrithioic acid),
poly(phosphorodiamidodithioic acid), and derivatives thereof (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: phosphoramidotrithioic
acid, phosphorodiamidodithioic acid, S-phenylphosphoramidotrithioic
acid, S-benzylphosphoramidotrithioic acid,
S-cyclohexylphosphoramidotrithioic acid,
S-norbornylphosphoramidotrithioic acid,
S,S'-diphenylphosphoramidot- ritbioic acid,
S,S'-dibenzylphosphoramidotrithioic acid,
S,S'-dicyclohexylphosphoramidotrithioic acid, and
S,S'-dinorbornylphospho- ramidotrithioic acid.
[0258] N--S Valence Stabilizer #8: Examples of phosphoramidothioic
acid, phosphoramidodithioic acid, phosphorodiamidothioic acid,
bis(phosphoramidothioic acid), bis(phosphoramidodithioic acid),
bis(phosphorodiamidothioic acid), poly(phosphoramidothioic acid),
poly(phosphoramidodithioic acid), and poly(phosphorodiamidothioic
acid) (N--S Bidentates and N--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphoramidothioic acid, phosphoramidodithioic acid,
phosphorodiamidothioic acid, phosphorohydrazidothioic acid,
phosphorohydrazidodithioic acid, phosphorodihydrazidothioic acid,
phosphoramidohydrazidothioic acid, O-phenylphosphoramidothioic
acid, O-benzylphosphoramidothioic acid,
O-cyclobexylphosphoramidothioic acid,
O-norbornylphosphoramidothioic acid, S-phenylphosphoramidodithioic
acid, S-benzylphosphoramidodithioic acid,
S-cyclohexylphosphoramidodithioic acid, and
S-norbornylphosphoramid- odithioic acid.
[0259] N--S Valence Stabilizer #9: Examples of N-thioacyl
7-aminobenzylidenimines (N--S Bidentates or N--S Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: N-thioacetyl 7-methylaminobenzylidenimine; N-thioacetyl
7-phenylaminobenzylidenimine; N-thiobenzoyl
7-methylaminobenzylidenimine; and N-thiobenzoyl
7-phenylaminobenzylidenimine.
[0260] N--S Valence Stabilizer #10: Examples of thiohydroxamates
(thiohydroxylamines), bis(thiohydroxamates), and
poly(thiohydroxamates) (N--S Bidentates, N--S Tetradentates, and
N--S Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: acetothiohydroxamic acid;
propianothiohydroxamic acid; butyrothiohydroxamic acid;
crotonothiohydroxamic acid; sorbothiohydroxamic acid;
benzothiohydroxamic acid; toluicthiohydroxamic acid;
salicylthiohydroxamic acid; phenylacetothiohydroxamic acid;
anthranilthiohydroxamic acid; nicotinethiohydroxamic acid;
picolinethiohydroxamic acid; cyclohexanethiohydroxamic acid;
quinoline 8-thiohydroxamic acid; cinnamylthiohydroxamic acid;
oxaldithiohydroxamic acid; succinylbis-N-phenylthiohydroxamic acid;
adipylbis-N-phenylthiohydroxamic acid; glyoxalthiohydroxamic acid;
2-thiophenethiocarbohydroxamic acid; thenoylthiohydroxamic acid;
N-phenylbenzothiohydroxamic acid; N-tolylbenzothiohydroxamic acid;
N-phenylacetothiohydroxamic acid; N-phenyl-2-thenoylthiohydroxamic
acid; and N-tolyl-2-thenoylthiohydroxami- c acid.
[0261] N--S Valence Stabilizer #11: Examples of alpha- or
ortho-aminothiocarboxylic acids, and alpha- or
ortho-aminothiodicarboxyli- c acids, and derivatives thereof (N--S
Bidentates, N--S Tridentates, and N--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2-pyridinethiocarboxylic acid (thiopicolinic acid);
2-pyrazinethiocarboxylic acid; o-aminothiobenzoic acid;
o-aminothionaphthoic acid; and 3,6-diaminothiophthalic acid.
[0262] N--S Valence Stabilizer #12: Examples of thiosemicarbazones,
bis(thiosemicarbazones), and poly(thiosemicarbazones) (N--S
Bidentates, N--S Tetradentates, and N--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetaldehyde thiosemicarbazone; acetone thiosemicarbazone;
pinacolone thiosemicarbazone; benzaldehyde thiosemicarbazone;
naphthaldehyde thiosemicarbazone; norbornanone thiosemicarbazone;
camphor thiosemicarbazone; nopinone thiosemicarbazone;
2-pyridinaldehyde thiosemicarbazone; salicylaldehyde
thiosemicarbazone; quinolinaldehyde thiosemicarbazone; isatin
dithiosemicarbazone; camphorquinone dithiosemicarbazone;
camphorquinone dithiosemicarbazone; picolinaldehyde
thiosemicarbazone; dipyridyl glyoxal dithiosemicarbazone;
di-2-pyridyl ketone thiosemicarbazone; methyl-2-pyridyl ketone
thiosemicarbazone; glyoxal dithiosemicarbazone; acetophenone
thiosemicarbazone; biacetyl monoxime thiosemicarbazone;
acetamidobenzaldehyde thiosemicarbazone;
thymolaldothiosemicarbazone; thiophene-2-aldehyde
thiosemicarbazone; phthalaldehyde dithiosemicarbazone; phthalimide
dithiosemicarbazone; furaldehyde thiosemicarbazone; naphthoquinone
thiosemicarbazone; phenanthrequinone thiosemicarbazone;
cyclohexanedione dithiosemicarbazone; ionone thiosemicarbazone;
bisthiosemicarbazone of diethyl-3,4-dioxadioate; pyridoxal
alkylthiosemicarbazones; benzylidene phenylthiosemicarbazones;
lawsone thiosemicarbazone; and 1-benzoin-4-phenylthiosemicarbazone
(bps).
[0263] N--S Valence Stabilizer #13: Examples of thioacyl
hydrazones, bis(thioacyl hydrazones), and poly(thioacyl hydrazones)
(N--S Bidentates, N--S Tetradentates, and N--S Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetaldehyde N-thioformylhydrazone; acetaldehyde
N-thiobenzoylhydrazone; acetone N-thioformylhydrazone; acetone
N-thiobenzoylhydrazone; pinacolone N-thioformylhydrazone;
pinacolone N-thiobenzoylhydrazone; benzaldehyde
N-thioformylhydrazone; benzaldehyde N-thiobenzoylhydrazone;
naphthaldehyde N-thioformylhydrazone; naphthaldehyde
N-thiobenzoylhydrazone; norbornanone N-thioformylhydrazone;
norbornanone N-thiobenzoylhydrazone; camphor N-thioformylhydrazone;
camphor N-thiobenzoylhydrazone; nopinone N-thioformylhydrazone;
nopinone N-thiobenzoylhydrazone; 2-pyridinaldehyde
N-thioformylhydrazone; 2-pyridinaldehyde N-thiobenzoylhydrazone;
salicylaldehyde N-thioformylhydrazone; salicylaldehyde
N-thiobenzoylhydrazone; quinolinaldehyde N-thioformylhydrazone;
quinolinaldehyde N-thiobenzoylhydrazone; thiophene-2-aldehyde
N-thioformylhydrazone; thiophene-2-aldehyde N-thiobenzoylhydrazone;
naphthoqui none N-thioformylhydrazone; naphthoqui none
N-thiobenzoylhydrazone; ionone N-thioformylhydrazone; ionone
N-thiobenzoylhydrazone; benzaldehyde benzothiazolehydrazone;
lawsone N-thioformylhydrazone; and lawsone
N-thiobenzoylhydrazone.
[0264] N--S Valence Stabilizer #14: Examples of thiocarbazones
(diazenecarbothioic hydrazides), bis(thiocarbazones), and
poly(thiocarbazones) (N--S Bidentates, N--S Tetradentates, and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diphenylthiocarbazone (dithizone);
2-phenylthiocarbazone; dinaphthylthiocarbazone;
2-naphthylthiocarbazone; and ambazone.
[0265] N--S Valence Stabilizer #15: Examples of azo compounds with
thiol or mercapto or thiocarbonyl substitution at the ortho- (for
aryl) or alpha- or beta- (for alkyl) positions, Bis[o-(HS--) or
alpha- or beta-(HS--)azo compounds], or Poly[o-(HS--) or alpha- or
beta-(HS--)azo compounds) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, or N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-thiolazobenzene
[1-(phenylazo)-2-thiophenol]; 2,2'-dithioazobenzene;
(2-thiophene)azobenzene; 1-(4-nitrophenylazo)-2-th- ionaphthol;
2-thiazolylazobenzene; and 2-benzothiazolylazobenzene.
[0266] N--S Valence Stabilizer #16: Examples of
diazeneformothioamides, diazeneacetothioamides,
bis(diazeneformothioamides), bis(diazeneacetothioamides),
poly(diazeneformothioamides), and poly(diazeneacetothioamides)
(N--S Bidentates, N--S Tetradentates, and N--S Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazeneformothioamide, diazeneacetothioamide,
phenyldiazeneformothioamide, diphenyldiazeneformothioamide,
phenyldiazeneacetothioamide, and diphenyldiazeneacetothioamide.
[0267] N--S Valence Stabilizer #117: Examples of diazenecarbothioic
acids, diazenecarbodithioic acids, bis(diazenecarbothioic acids),
bis(diazenecarbodithioic acids), poly(diazenecarbothioic acids),
poly(diazenecarbodithioic acids) and derivatives thereof (N--S
Bidentates, N--S Tetradentates, N--S Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazeneformothioic acid, diazeneacetothioic acid,
phenyldiazeneformothioic acid, diphenyldiazeneformothioic acid,
phenyldiazeneacetothioic acid, and diphenyldiazeneacetothioic
acid.
[0268] N--S Valence Stabilizer #18: Examples of
diazeneformothioaldehydes, diazeneacetothioaldehydes,
bis(diazeneformothioaldehydes), bis(diazeneacetothioaldehydes),
poly(diazeneformothioaldehydes), and
poly(diazeneacetothioaldehydes) (N--S Bidentates, N--S
Tetradentates and N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
diazeneformothioaldehyde, diazeneacetothioaldehyde,
phenyldiazeneformothioaldehyde, diphenyldiazeneformothioaldehyde,
phenyldiazeneacetothioaldehyde, and
diphenyldiazeneacetothioaldehyde.
[0269] N--S Valence Stabilizer #19: Examples of
diazenediformothioamides, diazenediacetothioamides,
bis(diazenediformothioamides), bis(diazenediacetothioamides),
poly(diazenediformothioamides), and poly(diazenediacetothioamides)
(N--S Tridentates and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
diazenediformodithioamide, diazenediacetodithioamide,
diphenydiazenediformodithioamide,
tetraphenyldiazenediformodithioamide,
diphenyldiazenediacetodithioamide, and
tetraphenyldiazenediacetodithioami- de.
[0270] N--S Valence Stabilizer #20: Examples of
diazenedicarbothioic acids, diazenedicarbodithioic acids,
bis(diazenedicarbothioic acids), bis(diazenedicarbodithioic acids),
poly(diazenedicarbothioic acids), poly(diazenedicarbodithioic
acids) and derivatives thereof (N--S Tridentates and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diazenediformothioic acid, diazenediacetodithioic
acid, phenyldiazenediformothioic acid, diphenyldiazenediformothioic
acid, phenyldiazenediacetodithioic acid, and
diphenyldiazenediacetodithioic acid.
[0271] N--S Valence Stabilizer #21: Examples of
diazenediformothioaldehyde- s, diazenediacetothioaldehydes,
bis(diazenediformothioaldehydes), bis(diazenediacetothioaldehydes),
poly(diazenediformothioaldehydes), and
poly(diazenediacetothioaldehydes) (N--S Tridentates and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diazenediformothioaldehyde,
diazenediacetothioaldehyde, diphenyldiazenediformothioaldehyde, and
diphenyldiazenediacetothioaldehyd- e.
[0272] N--S Valence Stabilizer #22: Examples of ortho-thio (or
-mercapto) substituted formazans, bis(o-thio or -mercapto
substituted formazans), and poly(o-thio or -mercapto substituted
formazans) (N--S Bidentates, N--S Tridentates, N--S Tetradentates,
and N--S Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 1-(2-thiophenyl)-3,5-di- phenylformazan;
1-(2-methylmercaptophenyl)-3,5-diphenylformazan;
1,5-bis(2-thiophenyl)-3-phenylformazan; and
5-bis(2-methylmercaptophenyl)- -3-phenyl formazan.
[0273] N--S Valence Stabilizer #23: Examples of ortho-thio (or
-mercapto) substituted azines (including ketazines), bis(o-thio or
mercapto substituted azines), and poly(o-thio or mercapto
substituted azines) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-mercapto-1-benzalazine; 2-mercapto-1-naphthalazine; and
2-mercapto-1-cyclohexanonazine.
[0274] N--S Valence Stabilizer #24: Examples of Schiff Bases with
one Imine (C.dbd.N) Group and with ortho- or alpha- or beta-thio or
mercapto or thiocarbonyl substitution (N--S Bidentates, N--S
Tridentates, N--S Tetradentates, N--S Pentadentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: N-(Thiosalicylaldehydo)- isopropylamine;
N-(2-thiophenecarboxaldehydo)isopropylamine;
N-(2-Acetylthiopheno)isopropylamine;
N-(2-Thioacetophenono)isopropylamine- ;
N-(Thiosalicylaldehydo)cyclohexylamine;
N-(2-Thiophenecarboxaldehydo)cyc- lohexylamine;
N-(2-Acetylthiopheno)cyclohexylamine;
N-(2-Thioacetophenono)cyclohexylamine;
N-(Thiosalicylaldehydo)aniline;
N-(2-Thiophenecarboxaldehydo)aniline; N-(2-Acetylthiopheno)aniline;
N-(2-Thioacetophenono)aniline;
N-(Thiosalicylaldehydo)aminonorbornane;
N-(2-Thiocarboxaldehydo)aminonorbornane;
N-(2-Acetylthiopheno)aminonorbor- nane;
N-(2-Thioacetophenono)aminonorbornane;
4-aminobenzylidene-3-propyl-5- -mercapto-1,2,4-triazole;
4-aminocinnamalidene-3-propyl-5-mercapto-1,2,4-t- riazole (acpmt);
4-aminosalicylidene-3-propyl-5-mercapto-1,2,4-triazole (aspmt);
4-aminovanillidene-3-propyl-5-mercapto-1,2,4-triazole;
4-aminodimethylaminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole
(adpmt); cinnamylideneaminophenylthiazole;
N-(2-mercaptophenyl)salicylide- nimine; 2-thiophenecarboxaldehyde
phenylhydrazone; 2-thiophenecarboxaldehy- de 2-pyridyl hydrazone;
2-mercaptobenzaldehyde phenylhydrazone; and 2-mercaptobenzaldehyde
2-pyridyl hydrazone. Also includes Schiff Bases derived from the
reaction of carbonyl compounds with dithiocarbazates, and
hydrazones with ortho-S substitution.
[0275] N--S Valence Stabilizer #25: Examples of Schiff Bases with
two Imine (C.dbd.N) Groups and with ortho- or alpha- or beta-thio
or mercapto or thiocarbonyl substitution (N--S Tridentates, N--S
Tetradentates, N--S Pentadentates, or N--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N'-(2,5-Thiophenedicarboxaldehydo)diis- opropylamine;
N,N'-(2,5-Thiophenedicarboxaldehydo)dicyclohexylamine;
N,N'-(2,5-Thiophenedicarboxaldehydo)dianiline;
N,N'-(2,5-Thiophenedicarbo- xaldehydo)di-aininonorbornane;
N,N'-(o-Thiophthalicdialdehydo)diisopropyla- mine;
N,N'-(o-Thiophthalicdialdehydo)dicyclohexylamine;
N,N'-(o-Thiophthalicdialdehydo)dianiline;
N,N'-(o-Thiophthalicdialdehydo)- di-aminonorbornane;
N,N'-(o-Thioformylcamphoro)diisopropylamine;
N,N'-(o-Thioformylcamphoro)dicyclohexyl amine;
N,N'-(o-Thioformylcamphoro- )dianiline;
N,N'-(o-Thioformylcamphoro)di-aminonorbornane;
N,N'-(o-Thiodiacetylbenzeno)diisopropylamine;
N,N'-(o-Thiodiacetylbenzeno- )dicyclohexylamine;
N,N'-(o-Thiodiacetylbenzeno)dianiline;
N,N'-(o-Thiodiacetylbenzeno)di-aminonorbornane;
N,N'-(3,6-Dithio-1,2-cycl- ohexanono)diisopropylamine;
N,N'-(3,6-Dithio-1,2-cyclohexanono)dicyclohexy- lamine;
N,N'-(3,6-Dithio-1,2-cyclohexanono)dianiline;
N,N'-(3,6-Dithio-1,2-cyclohexanono)di-aminonorbornane;
N,N'-(2,5-Diacetylthiopheno)diisopropylamine;
N,N'-(2,5-Diacetylthiopheno- )dicyclohexylamine;
N,N'-(2,5-Diacetylthiopheno)dianiline;
N,N'-(2,5-Diacetylthiopheno)di-aminonorbornane;
N,N'-(Thiosalicylaldehydo- )ethylenediamine;
N,N'-(o-Thionaphthaldehydo)ethylenediamine;
N,N'-(o-Thioacetophenono)ethylenediamine;
N,N'-(Thiosalicylaldehydo)trime- thylenediamine;
N,N'-(o-Thionaphthaldehydo)trimethylenediamine;
N,N'-(o-Thioacetophenono)trimethylenediamine;
N,N'-(Thiosalicylaldehydo)c- yclohexane-1,2-diamine;
N,N'-(o-Thionaphthaldehydo)cyclohexane-1,2-diamine- ;
N,N'-(o-Thioacetophenono)cyclohexane-1,2-diamine;
N,N'-(Thiosalicylaldehydo 1,2-diaminobenzene;
N,N'-(o-Thionaphthaldehydo)- -1,2-diaminobenzene; and
N,N'-(o-Thioacetophenono)-1,2-diaminobenzene. Also includes Schiff
Bases derived from the reaction of carbonyl compounds with
dithiocarbazates, and hydrazones with ortho-S substitution.
[0276] N--S Valence Stabilizer #26: Examples of Schiff Bases with
three Imine (C.dbd.N) Groups and with ortho- or alpha- or beta-thio
or mercapto or thiocarbonyl substitution (N--S Tetradentates, N--S
Pentadentates, or N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
N,N',N"-(Thiosalicylaldehydo)tris(2-aminoethyl)amine;
N,N',N"-(o-Thionaphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N"-(o-Thioacetopbenono)tris(2-aminoethyl)amine. Also includes
Schiff Bases derived from the reaction of carbonyl compounds with
dithiocarbazates, and hydrazones with ortho-S substitution.
[0277] N--S Valence Stabilizer #27: Examples of thioalkyl amines
(aminothiols or aminodisulfides) and thioalkyl imines (iminothiols
or iminodisulfides) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-mercapto-1-aminoethane; 2-methylmercapto-1-aminoethane;
3-mercapto-1-aminopropane; 1-mercapto-2-amino-2-methylpropane;
2-mercaptocyclohexylamine; 3-mercapto-2-aminonorbornane;
1,3-dimercapto-2-aminopropane; 1,5-dimercapto-3-aminopentane;
2,2'-diaminodiethyl sulfide; 3,3'-diaminodipropyl sulfide;
2,2'-diaminodicyclohexyl sulfide; 1,6-dimercapto-3,4-diaminohexane;
1,7-dimercapto-3,5-diaminoheptane;
1,6-diamino-3,4-dimercaptohexane;
1,7-diamino-3,5-dimercaptoheptane; tri(mercaptomethyl)amine;
tri(2-mercaptoethyl)amine; dithiooxamide (rubeanic acid);
2,2'-diaminodiethyl disulfide; 3,3'-diaminodipropyl disulfide;
2,2'-diaminodicyclohexyl disulfide;
3-amino-1,5-pentanedithiodialdehyde;
3,4-diamino-1,6-hexanedithiodialdehyde;
3,5-diamino-1,7-heptanedithiodial- dehyde; iminobisacetic acid;
iminobispropionic acid; and bis(hydroxyethyl)aminoalkyl
sulfide.
[0278] N--S Valence Stabilizer #28: Examples of thioaryl amines and
thioaryl imines (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-aminothiophenol
(2-aminobenzenethiol); 2-aminothiobenzoic acid (thioanthranilic
acid); 2-aminothioanisole; 2-(methanamine)benzyl mercaptan
[(2-aminomethyl)-alpha-toluenethiol] [(2-mercaptomethyl)-alpha--
aminotoluene]; 1-amino-2-naphthalenethiol;
2-amino-1-naphthalenethiol; 2-amino-1-(methyldisulfido)benzene;
2,2'-di(aminomethyl)diphenylthioketon- e; di(2-amino)phenyl
sulfide; di(2-amino)phenyl disulfide (di-ortho-aminophenyl
disulfide (doapd)); 1,3-di(2-amino)phenyl-2-mercapt- opropane;
1,3-di(3-amino)phenyl-2-mercaptopropane; 1,3-di(2-mercapto)pheny-
l-2-aminopropane; 1,3-di(3-mercapto)phenyl-2-aminopropane;
2,2'-dimercaptoiminodibenzyl; 2,2'-iminodibenzothioic acid;
2,2'-dimercaptoiminostilbene; and poly(o-aminothiophenol).
[0279] N--S Valence Stabilizer #29: Examples of five-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional sulfur atom binding site not in a
ring (N--S Bidentates, N--S Tridentates, N--S Tetradentates, or
N--S Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 2-mercaptopyrrole;
2-(methylthio)methylpyrrole; 2,5-(thiomethyl)pyrrole;
2,5-(methylthiomethyl)pyrrole; 2,6(methyldisulfidomethyl)pyrrole;
imidazoline-2-thione (2-mercaptoimidazole); 2-mercaptothiazoline;
2-mercaptobenzimidazole; 2-mercaptobenzothiazole;
2-mercaptobenzoxazole; 2-thiohydantoin; di-2-pyridylthioglyoxal
(2,2'-thiopyridil); bis((1-pyrazolyl)methane)sulfide;
bis((1-pyrazolyl)methane)disulfide;
bis(2-(1-pyrazolyl)ethane)sulfide;
bis(2-(1-pyrazolyl)ethane)disulfide;
bis(benzimidazolylmethane)sulfide;
bis(benzimidazolylethane)sulfide;
bis(benzimidazolylmethane)disulfide;
bis(benzimidazolylethane)disulfide; tris(imidazolyl)methanethiol;
tris(imidazolylmethane)methanethiol;
N-thiomethyl-N,N-(benzimidazolylmetbane)amine;
N-(2-thioethyl)-N,N-(benzi- midazolylmethane)amine;
N,N'-di(benzimidazolylmethane)-1,3-diamino-2-merca- ptopropane;
N,N,N',N'-tetrakis(benzimidazolylmethane)-1,3-diamino-2-mercap-
topropane; bis(N,N-((4-imidazolyl)methane)2-aminoethane)sulfide;
bis(N,N-((4-imidazolyl)methane)2-aminoethane)disulfide;
2-aminobenzothiazole (abt); 2-phenylaminothiazole; thiohydantoin;
thioxohydropyrazole; 2-mercaptobenzothiazole (mbt);
2-mercapto-1,3,4-thiadiazole; 2,5-dimercapto-1,3,4-thiadiazole
(bismuthiol); 2,5-bis(alkylthio)-1,3,4-thiadiazole;
2-amino-5-mercapto-1,3,4-thiadiazole (amt); 5-mercaptotetrazole;
1-phenyl-5-mercaptotetrazole (pmt)(5-mptt); 5-mercaptotriazole;
3-mercaptotriazole; (2-benzothiazolyl)thioacetic acid;
(2-benzothiazolyl)thiopropionic acid; (alkylthio)benzotriazoles;
(arylthio)benzotriazoles; 2-mercaptopyrimidine;
bis(5-mercapto-1,2,4-tria- zol-3-yl);
bis(5-mercapto-1,2,4-triazol-3-yl)alkanes; 2-aminothiazolidine;
thiazolidine-2-thione; 2-mercaptothiazolidine;
1-(2-mercaptoethyl)imidazo- line; imidazolidine-2-thione;
4,5-dihydroxyimidazolidine-2-thione;
4-amino-5-mercapto-1,2,4-triazole; (2-benzimidazolylthio)carboxylic
acids; (2-benzoxazolylthio)carboxylic acids;
(2-benzothiazolylthio)carbox- ylic acids;
(2-benzimidazolylthio)hydroxyalkyl(aryl)s;
(2-benzoxazolylthio)hydroxyalkyl(aryl)s; (2-benzothiazolylthio)
hydroxyalkyl(aryl)s; 2-(phenylmethylthio)benzothiazole;
2,5-bis(hydrocrarbyldithio 1,3,4-thiadiazoles;
2-(hydroarbyldithio)-5-mer- capto-1,3,4-thiadiazoles; bis(dithiobi
sthiadiazole); benzothi azolethione;
3-hydrazino-5-thio-1,2,4-triazole; imidazolidine-2,4-dithion- e;
dimercaptobenzothi azole; 2-aminothiazole (atz);
thiadiazole-2-thione; 5-mercaptothiadiazole-2-thione;
1,1-thiocarbonyldiimidazole;
phosphosphonomethylenethio-1,3-benzothiazole (pmtbt);
4,5-dihydroxyimidazolidine-2-thione; imidazolidine-2-thione;
1,1'-thiocarbonyldiimidazole; 2,2'-dithiobis(benzothiazole); and
5,5'-dithiobis(tetrazole).
[0280] N--S Valence Stabilizer #30: Examples of six-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional sulfur atom binding site not in a
ring (N--S Bidentates, N--S Tridentates, N--S Tetradentates, or
N--S Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 4-aminomethyl-3-pyridin- emethanethiol
(including thiopyridoxamine); 2-mercaptopyridine;
2-(methylthio)methylpyridine; 2-(2-(methylthio)ethyl)pyridine;
2,6-(thiomethyl)pyridine; 2,6-(methylthiomethyl)pyridine;
2,6-(methyldisulfidomethyl)pyridine; 2-mercaptopyrimidine;
2-dithiomethylpyrimidine; 2-mercaptoquinoline; 8-mercaptoquinoline
(thioxine); 8-methylthioquinoline; 2-mercaptoquinazoline;
thioorotic acid
(1,2,3,6-tetrahydro-2,6-dithiono-4-pyrimidinecarboxylic acid)
(6-thiouracilcarboxylic acid); 1-methylpyrimidine-2-thione;
2-thiouracil; 2,4-dithiouracil; 6-mercaptopurine;
bis(N,N,N',N'-tetra(2-(2-pyridyl)etha- ne)aminomethane)sulfide;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminometh- ane)disulfide;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminoethane)sulfide- ;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminoethane)disulfide;
1,3,5-triazine-6-thione; 2-benzylmercapto-1,3,5-triazine; triazine
dithiols [i.e. 6-(phenylamino)-1,3,5-triazine-2,4-dithiol (ptd);
6-aniline-1,3,5-triazine-2,4-dithiol (atd); and
2-(N,N-dialkylamino)-1,3,- 5-triazine-4,6-dithiol];
2-thioquinazoline; 2-thioquinazolin-4-one; thiomorpholin-3-thione;
[2-(aminomethyl)thio]pyridine; 6-mercaptopurine; dithiouracil; and
2,2'-dithiodipyridine (2,2'-dipyridyl disulfide).
[0281] N--S Valence Stabilizer #31: Examples of five-membered
heterocyclic rings containing one or two sulfur atoms at least one
additional nitrogen atom binding site not in a ring (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-aminothiophene; 2,5-diaminothiophene;
2-aminomethylthiophene; 2,5-di(aminomethyl)thiophene;
2-aminobenzothiophene; and 2-iminothiolane.
[0282] N--S Valence Stabilizer #32: Examples of six-membered
heterocyclic rings containing one or two sulfur atoms at least one
additional nitrogen atom binding site not in a ring (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-aminothiopyran; 2,6-diaminothiopyran;
2-aminomethylthiopyran; 2,6-di(aminomethyl)thiopyran; and
2-aminobenzothiopyran.
[0283] N--S Valence Stabilizer #33: Examples of five-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional sulfur atom binding site in a
separate ring (N--S Bidentates, N--S Tridentates, N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-(2-thiophene)pyrrole; 2,5-di(2-thiophene)pyrrole;
2-(2-thiopyran)pyrrole; 2,5-di(2-thiopyran)pyrrole;
2,5-di(2-pyrrole)thiophene; 2,6-di(2-pyrrole)thiopyran; and
3,5-bis(2-thienyl)-4-amino-1,2,4-triazole (2-tat).
[0284] N--S Valence Stabilizer #34: Examples of six-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional sulfur atom binding site in a
separate ring (N--S Bidentates, N--S Tridentates, N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-(2-thiadiazolyl)benzimidazole;
2-(2-thiophene)pyridine; 2,6-di(2-thiophene)pyridine;
2-(2-thiopyran)pyridine; 2,6di(2-thiopyran)pyridine;
2,5-di(2-pyridyl)thiophene; 2,6-di(2-pyridyl)thiopyran; and
2-(4-thiazolyl)benzimidazole.
[0285] N--S Valence Stabilizer #35: Examples of two-, three-,
four-, six-, eight-, and ten-membered macrocyclics, macrobicyclics,
and macropolycyclics (including catapinands, cryptands, cyclidenes,
and sepulchrates) wherein all binding sites are composed of
nitrogen (usually amine or imine groups) or sulfur (usually thiols,
mercaptans, or thiocarbonyls) and are not contained in component
heterocyclic rings (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: azathiacyclobutane
([4]aneNS); azathiacyclopentane ([5]aneNS); azathiacyclohexane
([6]aneNS); azathiacycloheptane ([7]aneNS); azathiacyclooctane
([8]aneNS); azathiacyclobutene ([4]eneNS); azathiacyclopentene
([5]eneNS); azathiacyclohexene ([6]eneNS); azathiacycloheptene
([7]eneNS); azathiacyclooctene ([8]eneNS); azathiacyclobutadiene
([4]dieneNS); azathiacyclopentadiene ([5]dieneNS);
azathiacyclohexadiene ([6]dieneNS); azathiacycloheptadiene
([7]dieneN S); azathiacyclooctadiene ([8]dieneNS);
diazathiacyclohexane ([6]aneSN.sub.2); diazathiacycloheptane
([7]aneSN.sub.2); diazathiacyclooctane ([8]aneSN.sub.2);
diazathiacyclononane ([9]aneSN.sub.2); diazathiacyclodecane
([10]aneSN.sub.2); diazathiacycloundecane ([11]aneSN.sub.2);
diazathiacyclododecane ([12]aneSN.sub.2); diazathiacyclohexene
([6]eneSN.sub.2); diazathiacycloheptene ([7]eneSN.sub.2);
diazathiacyclooctene ([8]eneSN.sub.2); diazathiacyclononene
([9]eneSN.sub.2); diazathiacyclodecene ([10]eneSN.sub.2);
diazathiacycloundecene ([11]eneSN.sub.2); diazathiacyclododecene
([12]eneSN.sub.2); diazadithiacyclooctane ([8]aneS.sub.2N.sub.2);
diazadithiacyclononane ([9]aneS.sub.2N.sub.2);
diazadithiacyclodecane ([10]aneS.sub.2N.sub.2);
diazadithiacycloundecane ([11]aneS.sub.2N.sub.2);
diazadithiacyclododecan- e ([12]aneS.sub.2N.sub.2);
diazadithiacyclotridecane ([13]aneS.sub.2N.sub.2);
diazadithiacyclotetradecane ([14]aneS.sub.2N.sub.2);
diazadithiacyclopentadecane ([15]aneS.sub.2N.sub.2);
diazadithiacyclohexadecane ([16]aneS.sub.2N.sub.2);
diazadithiacycloheptadecane ([17]aneS.sub.2N.sub.2);
diazadithiacyclooctadecane ([18]aneS.sub.2N.sub.2);
diazadithiacyclononadecane ([19]aneS.sub.2N.sub.2);
diazadithiacycloeicosane ([20]aneS.sub.2N.sub.2)- ;
diazadithiacyclooctadiene ([8]dieneS.sub.2N.sub.2);
diazadithiacyclononadiene ([9]dieneS.sub.2N.sub.2);
diazadithiacyclodecadiene ([10]dieneS.sub.2N.sub.2);
diazadithiacycloundecadiene ([11]dieneS.sub.2N.sub.2);
diazadithiacyclododecadiene ([12]dieneS.sub.2N.sub.2);
diazadithiacyclotridecadiene ([13]dieneS.sub.2N.sub.2);
diazadithiacyclotetradecadiene ([14]dieneS.sub.2N.sub.2);
diazadithiacyclopentadecadiene ([15]dieneS.sub.2N.sub.2);
diazadithiacyclohexadecadiene ([16]dieneS.sub.2N.sub.2);
diazadithiacycloheptadecadiene ([17]dieneS.sub.2N.sub.2);
diazadithiacyclooctadecadiene ([18]dieneS.sub.2N.sub.2);
diazadithiacyclononadecadiene ([19]dieneS.sub.2N.sub.2);
diazadithiacycloeicosadiene ([20]dieneS.sub.2N.sub.2); and
tetramethyldithiahexaazacyclobidecanehexaene (mtab).
[0286] N--S Valence Stabilizer #36: Examples of four-, six-,
eight-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen or
sulfur and are contained in component heterocyclic rings (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiopyrandipyridines; dithiophenedipyrroles;
trithiopyrantripyridines; trithiophenetripyrroles;
tetrathiopyrantetrapyridines; and tetrathiophenetetrapyrroles.
[0287] N--S Valence Stabilizer #37: Examples of four-, six-,
eight-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen or
sulfur and are contained in a combination of heterocyclic rings and
amine, imine, thiol, mercapto, or thiocarbonyl groups (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: azathiatetraphyrins; diazadithiatetraphyrins;
azathiahexaphyrins; diazadithiahexaphyrins; and
triazatrithiahexaphyrins.
[0288] N--O Valence Stabilizer #1: Examples of N-hydroxy (or
N,N'-dihydroxy)amidines and N-hydroxy (or N,N'-dihydroxy)diamidines
(N--O bidentates, N--O tridentates, or N--O tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N-hydroxy-N,N'-dimethyl- fonmamidine;
N-hydroxy-N,N'-diethylformamidine; N-hydroxy-N,N'-diisopropyl-
formamidine; N-hydroxy-N,N'-dibutylfonmamidine;
N-hydroxy-N,N'-diphenylfor- mamidine;
N-hydroxy-N,N'-dibenzylformamidine; N-hydroxy-N,N'-dinaphthylfor-
mamidine; N-hydroxy-N,N'-dicyclohexylformamidine;
N-hydroxy-N,N'-dinorborn- ylformamidine;
N-hydroxy-N,N'-diadamantylformamidine;
N-hydroxy-N,N'-dianthraquinonylformamidine;
N-hydroxy-N,N'-dimethylacetam- idine;
N-hydroxy-N,N'-diethylacetamidine;
N-hydroxy-N,N'-diisopropylacetam- idine;
N-hydroxy-N,N'-dibutylacetamidine;
N-hydroxy-N,N'-diphenylacetamidi- ne;
N-hydroxy-N,N'-dibenzylacetamidine;
N-hydroxy-N,N'-dinaphthylacetamidi- ne;
N-hydroxy-N,N'-dicyclohexylacetamidine;
N-hydroxy-N,N'-dinorbornylacet- amidine;
N-hydroxy-N,N'-diadamantylacetamidine; N-hydroxy-N,N'-dimethylben-
zamidine; N-hydroxy-N,N'-diethylbenzamidine;
N-hydroxy-N,N'-diisopropylben- zamidine;
N-hydroxy-N,N'-dibutylbenzamidine; N-hydroxy-N,N'-diphenylbenzam-
idine; N-hydroxy-N,N'-dibenzylbenzamidine;
N-hydroxy-N,N'-dinaphthylbenzam- idine;
N-hydroxy-N,N'-dicyclohexylbenzamidine;
N-hydroxy-N,N'-dinorbornylb- enzamidine;
N-hydroxy-N,N'-diadamantylbenzamidine; N-hydroxy-N,N'-dimethyl-
toluamidine; N-hydroxy-N,N'-diethyltoluamidine;
N-hydroxy-N,N'-diisopropyl- toluamidine;
N-hydroxy-N,N'-dibutyltoluamidine; N-hydroxy-N,N'-diphenyltol-
uamidine; N-hydroxy-N,N'-dibenzyltoluamidine;
N-hydroxy-N,N'-dinaphthyltol- uamidine;
N-hydroxy-N,N'-dicyclohexyltoluamidine; N-hydroxy-N,N'-dinorborn-
yltoluamidine; N-hydroxy-N,N'-diadamantyltoluamidine;
N,N-dihydroxyoxalic diamidine; N,N'-dihydroxymalonic diamidine;
N,N'-dihydroxysuccinic diamidine; N,N'-dihydroxyglutaric diamidine;
N,N'-dihydroxyadipic diamidine; N,N'-dihydroxypimelic diamidine;
N,N'-dihydroxysuberic diamidine; N,N'-dihydroxyphthalic diamidine;
N,N'-dihydroxyterephthalic diamidine; N,N'-dihydroxyisophthalic
diamidine; N,N'-dihydroxypiperazine diamidine.
[0289] N--O Valence Stabilizer #2: Examples of guanylureas,
guanidinoureas, bis(guanylureas), bis(guanidinoureas)
poly(guanylureas), and poly(guanidinoureas) (N--O Bidentates and
N--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: guanylurea (amidinourea)(dicyandiamidine);
guanidinourea; methylguanylurea; ethylguanylurea;
isopropylguanylurea; butylguanylurea; benzylguanylurea;
phenylguanylurea; tolylguanybrea; naphthylguanylurea;
cyclohexylguanylurea; norbornylguanylurea; adamantylguanylurea;
dimethylguanylurea; diethylguanylurea; diisopropylguanylurea;
dibutylguanylurea; dibenzylguanylurea; diphenylguanylurea;
ditolylguanylurea; dinaphthylguanylurea; dicyclohexylguanylurea;
dinorbornylguanylurea; diadamantylguanylurea;
ethylenebis(guanylurea); propylenebis(guanylurea);
phenylenebis(guanylurea); piperazinebis(guanylurea);
oxalylbis(guanylurea); malonylbis(guanylurea);
succinylbis(guanylurea); phthalylbis(guanylurea); 2-ureidothiazole;
2-ureidooxazole; 2-ureidoimidazole; 3-ureidopyrazole;
3-ureido-1,2,4-triazole; and 5-ureidotetrazole.
[0290] N--O Valence Stabilizer #3: Examples of amidinoamides,
guanidinoamides, bis(amidinoamides), bis(guanidinoamides),
poly(amidinoamides), and poly(guanidinoamides) (including both
N-amidinoamides and 2-amidinoacetamides) (N--O Bidentates, N--O
Tridentates, and N--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: amidinoacetamide
(1-acetylguanidine); guanidinoacetamide; amidinopropanamide;
amidinobutanamide; amidinobenzamide; amidinotoluamide;
amidinocyclohexamide; N-methylamidinoacetamide;
N-ethylamidinopropanamide; N-propylamidinobutanamide;
N-phenylamidinobenzamide; N-tolylamidinotoluamide;
N-cyclohexylamidinocyclohexamide; bis(amidinooxamide);
bis(amidinomalonamide); bis(amidinosuccinamide);
bis(amidinophthalamide); 2-amidinoacetamide (malonamamidine);
N-methyl-2-amidinoacetamide; N-ethyl-2-amidinoacetamide;
N-phenyl-2-amidinoacetamide; N-benzyl-2-amidinoacetamide;
N-cyclohexyl-2-amidinoacetamide; N,N'-dimethyl-2-amidinoacetamide;
N,N'-diethyl-2-amidinoacetamide; N,N'-diphenyl-2-amidinoacetamide;
N,N'-dibenzyl-2-amidinoacetamide;
N,N'-dicyclohexyl-2-amidinoacetamide; 2-N-acylaminothiazole;
2-N-acylaminooxazole; 2-N-acylaminoimidazole;
3-N-acylaminopyrazole; 3-N-acylamino-1,2,4-triazole; and 5-N-acyl
aminotetrazole.
[0291] N--O Valence Stabilizer #4: Examples of imidoylamides,
bis(imidoylamides), and poly(imidoylamides) (N--O Bidentates, N--O
Tridentates, and N--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: acetimidoylacetamide;
acetimidoylpropanamide; acetimidoylbutanamide;
acetimidoylbenzamide; acetimidolytoluamide;
acetimidoylcyclohexamide; propimidoylpropanamide;
butimidoylbutanamide; benzimidoylbenzamide;
ethylenebis(acetimidoylacetam- ide);
propylenebis(acetimidoylacetamide); and
phenylenebis(acetimidoylacet- amide).
[0292] N--O Valence Stabilizer #5: Examples of O-amidinocarbamates,
bis(O-amidinocarbamates), and poly(O-amidinocarbamates) (N--O
Bidentates and N--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: O-amidinocarbamate;
N-methyl-O-amidinocarbamate; N-ethyl-O-amidinocarbamate;
N-isopropyl-O-amidinocarbamate; N-butyl-O-amidinocarbamate;
N-benzyl-O-amidinocarbamate; N-phenyl-O-amidinocarbamate;
N-tolyl-O-amidinocarbamate; N-naphthyl-O-amidinocarbamate;
N-cyclohexyl-O-amidinocarbamate; N-norbornyl-O-amidinocarbamate;
N-adamantyl-O-amidinocarbamate; N,N'-dimethyl-O-amidinocarbamate;
N,N'-diethyl-O-amidinocarbamate;
N,N'-diisopropyl-O-amidinocarbamate;
N,N'-dibutyl-O-amidinocarbamate; N,N'-dibenzyl-O-amidinocarbamate;
N,N'-diphenyl-O-amidinocarbamate; N,N'-ditolyl-O-amidinocarbamate;
N,N'-dinaphthyl-O-amidinocarbamate;
N,N'-dicyclohexyl-O-amidinocarbamate;
N,N'-dinorbornyl-O-amidinocarbamate- ;
N,N'-diadamantyl-O-amidinocarbamate;
ethylenebis(O-amidinocarbamate); propylenebis(O-amidinocarbamate);
phenylenebis(O-amidinocarbamate);
piperazinebis(O-amidinocarbamate); oxalylbis(O-amidinocarbamate);
malonylbis(O-amidinocarbamate); succinylbis(O-amidinocarbamate);
phthalylbis(O-amidinocarbamate); 2-O-carbamatothiazole;
2-O-carbamatooxazole; 2-O-carbamatoimidazole;
3-O-carbamatopyrazole; 3-O-carbamato-1,2,4-triazole; and
5-carbamatotetrazole.
[0293] N--O Valence Stabilizer #6; Examples of
S-amidinothiocarbamates, bis(S-amidinothiocarbamates), and
poly(S-amidinothiocarbamates) (N-O Bidentates and N--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: S-amidinothiocarbamate; N-methyl-S-amidinothiocar-
bamate; N-ethyl-S-amidinothiocarbamate;
N-isopropyl-S-amidinothiocarbamate- ;
N-butyl-S-amidinothiocarbamate; N-benzyl-S-amidinothiocarbamate;
N-phenyl-S-amidinothiocarbamate; N-tolyl-S-amidinothiocarbamate;
N-naphthyl-S-amidinothiocarbamate;
N-cyclohexyl-S-amidinothiocarbamate;
N-norbornyl-S-amidinothiocarbamate;
N-adamantyl-S-amidinothiocarbamate;
N,N'-dimethyl-S-amidinothiocarbamate;
N,N'-diethyl-S-amidinothiocarbamate- ;
N,N'-diisopropyl-S-amidinothiocarbamate;
N,N'-dibutyl-S-amidinothiocarba- mate;
N,N'-dibenzyl-S-amidinothiocarbamate;
N,N'-diphenyl-S-amidinothiocar- bamate;
N,N'-ditolyl-S-amidinothiocarbamate; N,N'-dinaphthyl-S-amidinothio-
carbamate; N,N'-dicyclohexyl-S-amidinothiocarbamate;
N,N'-dinorbornyl-S-amidinothiocarbamate;
N,N'-diadamantyl-S-amidinothioca- rbamate;
ethylenebis(S-amidinothiocarbamate); propylenebis(S-amidinothioca-
rbamate); phenylenebis(S-amidinothiocarbamate);
piperazinebis(S-amidinothi- ocarbamate);
oxalylbis(S-amidinothiocarbamate); malonylbis(S-amidinothioca-
rbamate); succinylbis(S-amidinothiocarbamate);
phthalylbis(S-amidinothioca- rbamate);
2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole;
2-O-monothiocarbamatoimidazole; 3-O-monothiocarbamatopyrazole;
3-O-monothiocarbamato-1,2,4-triazole; and
5-O-monothiocarbamatotetrazole.
[0294] N--O Valence Stabilizer #7: Examples of diimidosulfuric
acid, bis(diimidosulfuric acid), and derivatives thereof (N--O
Bidentates and N--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diimidosulfuric acid;
O-phenyldiimidosulfuric acid; O-benzyldiimidosulfuric acid,
O-cyclohexyldiimidosulfuric acid, O-norbornyldiimidosulfuric acid,
O,O'-diphenyldiimidosulfuric acid; O,O'-dibenzyldiimidosulfuric
acid, O,O'-dicyclohexyldiimidosulfuric acid, and
O,O'-dinorbornyldiimidosulfuric acid.
[0295] N--O Valence Stabilizer #8: Examples of phosphorimidic acid,
bis(phosphorimidic acid); and poly(phosphorimidic acid), and
derivatives thereof (N--O Bidentates, N--O Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphorimidic acid; O-phenylphosphorimidic acid;
O-benzylphosphorimidic acid; O-cyclohexylphosphorimidic acid;
O-norbornylphosphorimidic acid; O,O'-diphenylphosphorimidic acid;
O,O'-dibenzylphosphorimidic acid; O,O'-dicyclohexylphosphorimidic
acid; and O,O'-dinorbornylphosphorimidic acid.
[0296] N--O Valence Stabilizer #9: Examples of phosphoric
triamides, bis(phosphoric triamides), and poly(phosphoric
triamides) (N--O Bidentates and N--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphoric triamide; phosphoramidic dihydrazide; N-phenylphosphoric
triamide, N-benzylphosphoric triamide; N-cyclohexylphosphoric
triamide; N-norbornylphosphoric triamide; N,N'-diphenylphosphoric
triamide, N,N'-dibenzylphosphoric triamide;
N,N'-dicyclohexylphosphoric triamide; and
N,N'-dinorbornylphosphoric triamide.
[0297] N--O Valence Stabilizer #10: Examples of phosphoramidic
acid, phosphorodiamidic acid, bis(phosphoramidic acid),
bis(phosphorodiamidic acid), poly(phosphoramidic acid),
poly(phosphorodiamidic acid), and derivatives thereof (N--O
Bidentates and N--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: phosphoramidic acid,
phosphorodiamidic acid, phosphoramidohydrazidic acid;
phosphorohydrazidic acid; phosphorodihydrazidic acid;
O-phenylphosphoramidic acid; O-benzylphosphoramidic acid;
O-cyclohexylphosphoramidic acid; O-norbornylphosphoramidic acid;
O,O'-diphenylphosphoramidic acid; O,O'-dibenzylphosphoramidic acid;
O,O'-dicyclohexylphosphoramidic acid; and
O,O'-dinorbornylphosphoramidic acid.
[0298] N--O Valence Stabilizer #11: Examples of N-acyl
7-aminobenzylidenimines (N--O Bidentates or N--O Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: N-acetyl 7-methylaminobenzylidenimine; N-acetyl
7-phenylaminobenzylidenimine; N-benzoyl
7-methylaminobenzylidenimine; and N-benzoyl
7-phenylaminobenzylidenimine.
[0299] N--O Valence Stabilizer #12: Examples of oximes, dioximes,
and poly(oximes) (N--O Bidentates, N--O Tridentates, and N--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: acetaldoxime (Hado); acetoxime (acetone
oxime)(Hato); butanone oxime; pentanone oxime; hexanone oxime;
pinacolone oxime; heptanone oxime; octanone oxime; cyclopentanone
oxime; cyclohexanone oxime; cycloheptanone oxime; cyclooctanone
oxime; cyclopentanedione dioxime; cyclohexanedione dioxime;
cycloheptanedione dioxime; cyclooctanedione dioxime; isatin
dioxime; benzaldehyde oxime; naphthaldehyde oxime; norbornanone
oxime; camphor oxime; dimethylglyoxime (H.sub.2DMG);
diethylglyoxime; diisopropylglyoxime; ditertbutylglyoxime;
dicyanoglyoxime; dicyanamidoglyoxime; diphenylglyoxime (Hdfg);
dibenzylglyoxime; dicyclohexylglyoxime; dinorbornylglyoxime;
camphorquinone dioxime (Hcqd); nopinoquinone dioxime (Hnqd);
butyraldoxime; propionaldoxime; furildioxime; and
thienyldioxime.
[0300] N--O Valence Stabilizer #13: Examples of carbonyl oximes,
bis(carbonyl oximes), and poly(carbonyl oximes) (N--O Bidentates,
N--O Tridentates, and N--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diacetyl monoxime (2,3-butanedione monoxime); benzil monoxime
(1,2-diphenylethanedione monoxime); 1,2-dicyclohexylethanedione
monoxime; 1,2-(trifluoromethyl)ethanedione monoxime;
1,2-dinorbornylethanedione monoxime; cyclopentanedione monoxime;
cyclohexanedione monoxime; cycloheptanedione monoxime;
cyclooctanedione monoxime; camphorquinone oxime;
3-hydroxyiminopentane-2,- 4-dione; and 4-isonitrosopyralozone.
[0301] N--O Valence Stabilizer #14: Examples of imine oximes,
bis(imine oximes), and poly(imine oximes) (including 2-nitrogen
heterocyclic oximes) (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
3-(methylimino)butan-2-one oxime; 4-(methylimino)hexan-3-one oxime;
1,2-dipbenyl-2-(methylimino)ethan-1-one oxime;
1,2-diphenyl-2-(phenylimin- o)ethan-1-one oxime;
1,2-dicyclohexyl-2-(methylimino)ethan-1-one oxime;
1,2-dicyclohexyl-2-(cyclohexylimino)ethan-1-one oxime;
1,2-dinorbornyl-2-(methylimino)ethan-1-one oxime;
N,N'-methylenebis-(3-im- inobutan-2-one oxime);
N,N'-methylenebis-(4-iminohexan-3-one oxime);
N,N'-methylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime);
N,N'-methylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime);
N,N'-methylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime);
N,N'-ethylenebis-(3-iminobutan-2-one oxime);
N,N'-ethylenebis-(4-iminohex- an-3-one oxime);
N,N'-ethylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime);
N,N'-ethylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime);
N,N'-ethylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime);
N,N'-propylenebis-(3-iminobutan-2-one oxime);
N,N'-propylenebis-(4-iminoh- exan-3-one oxime);
N,N'-propylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime);
N,N'-propylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime);
N,N'-propylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime);
diacetylazine oxime (Hazio); 2-pyridinaldoxime (Hpao); methyl
2-pyridyl ketone oxime; ethyl 2-pyridyl ketoxime; phenyl 2-pyridyl
ketone oxime (Hppk); benzyl 2-pyridyl ketoxime; di(2-pyridyl)
ketone oxime; methyl 2-pyrrolyl ketone oxime; ethyl 2-pyrrolyl
ketone oxime; phenyl 2-pyrrolyl ketone oxime; di(2-pyrrolyl) ketone
oxime; and tris(2-aldoximo-6-pyridyl)- phosphine.
[0302] N--O Valence Stabilizer #15: Examples of hydroxy oximes,
bis(hydroxy oximes), and poly(hydroxy oximes) (including 2-oxygen
heterocyclic oximes) (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 3-hydroxybutan-2-one
oxime; 4-hydroxyhexan-3-one oxime; benzoin oxime
(bo)(1,2-diphenyl-2-hydroxyetha- none oxime);
1,2-di(trifluoromethyl)-2-hydroxyethanone oxime;
1,2-dicyclohexyl-2-hydroxyethanone oxime;
1,2-dinorbornyl-2-hydroxyethano- ne oxime; salicylaldoxime
(so)(saldox); 2-hydroxy-1-naphthaldehyde oxime; 2-furanaldoxime;
furildioxime; methyl 2-furanyl ketone oxime; ethyl 2-furanyl
ketoxime; phenyl 2-furanyl ketone oxime; benzyl 2-furanyl ketoxime;
di(2-furanyl) ketone oxime; and 2,5-(oximinomethyl)phenol.
[0303] N--O Valence Stabilizer #16: Examples of amino oximes,
bis(amino oximes), and poly(amino oximes) (N--O Bidentates, N--O
Tridentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
3-(methylamino)butan-2-one oxime (HMeabo);
4-(methylamino)hexan-3-one oxime (HEtabo);
1,2-diphenyl-2-(methylamino)ethanone oxime (HPhabo);
1,2-diphenyl-2-(phenylamino)ethanone oxime;
1,2-dicyclohexyl-2-(methylami- no)ethanone oxime (HcyHxabo);
1,2-dicyclohexyl-2-(cyclohexylamino)ethanone oxime;
1,2-di(trifluoromethyl)-2-(methylamino)ethanone oxime;
1,2-dinorbornyl-2-(methylamino)ethanone oxime (HNorbabo);
N,N'-ethylenebis-(3-aminobutan-2-one oxime)(Haboen);
N,N'-ethylenebis-(4-aminohexan-3-one oxime);
N,N'-ethylenebis-(1,2-diphen- yl-2-aminoethanone oxime);
N,N'-ethylenebis-(1,2-dicyclohexyl-2-aminoethan- one oxime);
N,N'-ethylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime);
N,N'-ethylenebis-(1,2-dinorbornyl-2-aminoethanone oxime);
N,N'-propylenebis-(3-aminobutan-2-one oxime)(Habopn);
N,N'-propylenebis-(4-aminohexan-3-one oxime);
N,N'-propylenebis-(1,2-diph- enyl-2-aminoethanone oxime);
N,N'-propylenebis-(1,2-dicyclohexyl-2-aminoet- hanone oxime);
N,N'-propylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime);
N,N'-propylenebis-(1,2-dinorbornyl-2-aminoethanone oxime);
2,2'-iminobis(acetamidoxime); 1-diethylamino-3-butanoxime; and
di-2-pyridyl ketone oxime.
[0304] N--O Valence Stabilizer #17: Examples of amido oximes,
bis(amido oximes), and poly(amido oximes) (N--O Bidentates, N--O
Tridentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
formamide oxime; acetamide oxime; propanamide oxime; butanamide
oxime; benzamide oxime (Hbamox); naphthamide oxime; diformamide
dioxime; salicylamide oxime; and 4-imidazolamide oxime.
[0305] N--O Valence Stabilizer #18: Examples of azo oximes, bis(azo
oximes), and poly(azo oximes) (N--O Bidentates, N--O Tridentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetaldehyde phenylhydrazone oxime; propionaldehyde phenylhydrazone
oxime; and benzaldehyde phenylhydrazone oxime. Also includes
hydrazone oximes.
[0306] N--O Valence Stabilizer #19: Examples of 2-nitrosophenols
(o-quinone monoximes) (N--O Bidentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-nitrosophenol;
1-nitroso-2-naphthol (Honn); 2-nitroso-1-naphthol (Htnn);
3-nitrosopyrocatechol; 3,6-dinitrosopyrocatechol;
2-nitrosoresorcinol; 2,4-dinitrosoresorcinol;
2,4,6-trinitrosoresorcinol; 2-nitrosohydroquinone;
2,6-dinitrosohydroquinone; 2,3,5,6-tetranitrosohydroquinone;
4-nitrosopyrogallol; 4,6-dinitrosopyrogallol;
2-nitrosophloroglucinol; 2,4,6-trinitrosophloroglucinol;
7-nitroso-6-hydroxyindazole; Pigment Green 12 (C.I. 10020);
Naphthol Green; and nitroso-R-salt.
[0307] N--O Valence Stabilizer #20: Examples of 2-nitrophenols
(N--O Bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-nitrophenol; 2,3-dinitrophenol;
2,4-dinitrophenol; 2,5-dinitrophenol; 2,6-dinitrophenol;
2,4,6-trinitrophenol (picric acid); 2-amino-4,6-dinitrophenol
(picramic acid); 1-nitro-2-naphthol; 2-nitro-1-naphthol;
3-nitropyrocatechol; 3,6-dinitropyrocatechol; 2-nitroresorcinol;
2,4-dinitroresorcinol; 2,4,6-trinitroresorcinol (styphnic acid);
2-nitrohydroquinone; 2,6-dinitrohydroquinone;
2,3,5,6-tetranitrohydroquinone; 4-nitropyrogallol;
4,6-dinitropyrogallol; 2-nitrophloroglucinol;
2,4,6-trinitrophloroglucinol; dinitrocresol;
7-nitro-6-hydroxyindazole; Dinoseb; Eosin; Naphthol Yellow; and
Martius Yellow.
[0308] N--O Valence Stabilizer #21: Examples of hydroxamates
(hydroxylamines), bis(hydroxamates), and poly(hydroxamates) (N--O
Bidentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetohydroxamic acid; propianohydroxamic acid; butyrohydroxamic
acid; crotonohydroxamic acid; sorbohydroxamic acid; benzohydroxamic
acid (BH.sub.2); toluichydroxamic acid; salicylhydroxamic acid
(SH.sub.2); phenylacetohydroxamic acid (PhH.sub.2);
anthranilhydroxamic acid (AnH.sub.2); nicotinehydroxamic acid
(NiCH.sub.2); picolinehydroxamic acid; cyclohexanehydroxamic acid
(CH.sub.2); quinoline 8-hydroxamic acid (QH.sub.2);
cinnamylhydroxamic acid (CnH.sub.2); oxaldihydroxamic acid
(OxalH.sub.2); succinylbis-N-phenylhydroxamic acid (SuH.sub.2);
adipylbis-N-phenylhydrox- amic acid (AdH.sub.2); glyoxalhydroxamic
acid (GH.sub.2); 2-tbiophenecarbohydroxamic acid; thenoylhydroxamic
acid; N-phenylbenzohydroxamic acid; N-tolylbenzohydroxamic acid;
N-phenylacetohydroxamic acid; N-phenyl-2-thenoylhydroxamic acid;
N-tolyl-2-thenoylhydroxamic acid; and polyhydroxamic acids.
[0309] N--O Valence Stabilizer #22: Examples of
N-nitrosohydroxylamines, bis(N-nitrosohydroxylamines), and
poly(N-nitrosohydroxylamines) (N--O Bidentates, N--O Tetradentates,
and N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: N-nitrosophenylhydroxyl- amine (cupferron);
N-nitrosonaphthylhydroxylamine (neocupferron);
N-nitrosoanthracylhydroxylamine; N-nitroso(2-pyridyl)hydroxylamine;
and N-nitroso(2-thiophenyl)hydroxylamine.
[0310] N--O Valence Stabilizer #23: Examples of amino acids,
ortho-aminocarboxylic acids, peptides, polypeptides, and proteins
[N--O Bidentates, N--O Tridentates, and N--O Tetradentates;
possibly S--O dentates for sulfur-contg. examples such as
penicillamine and cystine] that meet the requirements for use as
"wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: alanine (Ala); arginine (Arg);
asparagine (Asn); aspartic acid (Asp); cysteine (Cys); cystine (Cys
or Cys.Cys); dihydroxyphenylalanine (Dopa); glutamic acid (Glu);
glutamine (Gin); glycine (Gly); histidine (His); isoleucine (Ile);
leucine (Leu); lysine (Lys); methionine (Met); penicillamine (Pen);
phenylalanine (Phe); tolylalanine (tala); proline (Pro); sarcosine;
serine (Ser); threonine (Thr); tryptophan (Trp); tyrosine (Tyr);
and valine (Val) as amino acid examples; 2-pyridinecarboxylic acid
(picolinic acid), 2-pyrazinecarboxylic acid, 2,3-dicarboxypyrazine,
and anthranilic acid as ortho-aminocarboxylic acid examples;
Gly-GluO; Hgly-Gly; Gly-MetO; Met-GlyO; Gly-TyrO; Ala-H is O;
Gly-His-GlyO; Gly-Gly-His; Gly-Leu-TyrO; penta-GlyO; His-His;
triaminoisobutyrate; tetra-GlyO; Pro-Gly; and Gly-Met as peptide
examples; and azurin, carbonic anhydrase C; carboxypeptidase;
concanavalin A; cytochrome b; cytochrome c; erythrocruorin;
ferredoxin; haemerythrin; haemoglobin; myoglobin; parvalbumin;
albumin; plastocyanin; rubredoxin; superoxide dismutase;
thermolysin; and trysin as protein examples; N-acylamino acids;
aminocaproic acid; and 3,5-diiodotyrosine.
[0311] N--O Valence Stabilizer #24: Examples of amides,
bis(amides), and poly(amides), including lactams (N--O bidentates,
N--O tridentates, and N--O tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetamide; propionamide; butanamide; benzamide
(benzoylamide)(1-phenylformamide); 1-naphthylformamide; toluamide;
1-cyclohexylformamide); 1-norbornylformamide; 1-adamantylform
amide; N,N-dimethylformamide (DMF)(DMFA); N,N-dimethylacetamide
(DMAC); N,N-dimethylbenzamide; N,N-diethylformamide;
N,N-diethylacetamide; decanamide; dodecanamide; tetradecanamide;
hexadecanamide; octadecanamide; lactobionic acid amide;
(hydroxyalkylthio)succinamides; (mercaptoalkoxy)succinamides;
polycaproamides; glycinamide; aminoalkylanilides; amidopolyamines
(apa); bis(1-phenylethylamide); oxalic semiamide; malonic
semiamide; succinic semiamide;
bis(1,1'-benzotriazolyl)dicarboxamide; nicotinamide; acetanilide
(N-phenylacetamide); formanilide (N-phenylformamide); benzanilide
(N-phenylbenzamide); N-methylformanilide; acetanilide;
nicotinanilide; 4'-hydroxyacetanilide (acetaminophen);
2-pyrrolidone; methyl-2-pyrrolidone (NMP); 2-piperidone
(valerolactam); caprolactam; polymethylenepolyamine dipropionamide;
polyacrylamides; polypyrrolidones [including polyvinylpyrrolidone
(povidone)(PVP)]; pyrazolidinones; pyrazolones; diazepinones;
N-alkylazaalkene lactams; and N-(2-hydroxyalkyl)azaalkene
lactams.
[0312] N--O Valence Stabilizer #25: Examples of semicarbazones,
bis(semicarbazones), and poly(semicarbazones) (N--O Bidentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetaldehyde semicarbazone; acetone semicarbazone; pinacolone
semicarbazone; benzaldehyde semicarbazone; naphthaldehyde
semicarbazone; norbornanone semicarbazone; camphor semicarbazone;
nopinone semicarbazone; 2-pyridinaldehyde semicarbazone;
salicylaldehyde semicarbazone; quinolinaldehyde semicarbazone;
isatin disemicarbazone; camphorquinone disemicarbazone;
camphorquinone disemicarbazone; picolinaldehyde semicarbazone;
dipyridyl glyoxal disemicarbazone; di-2-pyridyl ketone
semicarbazone; methyl-2-pyridyl ketone semicarbazone; glyoxal
disemicarbazone; acetophenone semicarbazone; biacetyl monoxime
semicarbazone; acetamidobenzaldehyde semicarbazone;
thymolaldosemicarbazone; thiophene-2-aldehyde semicarbazone;
phthalaldehyde disemicarbazone; phthalimide disemicarbazone;
furaldehyde semicarbazone; naphthoquinone semicarbazone;
phenanthrequinone semicarbazone; cyclohexanedione disemicarbazone;
ionone semicarbazone; bissemicarbazone of diethyl-3,4-dioxadioate;
and lawsone semicarbazone.
[0313] N--O Valence Stabilizer #26: Examples of acyl hydrazones,
bis(acyl hydrazones), and poly(acyl hydrazones) (N--O Bidentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetaldehyde N-formylhydrazone; acetaldehyde N-benzoylhydrazone;
acetone N-formylhydrazone; acetone N-benzoylhydrazone; pinacolone
N-formylhydrazone; pinacolone N-benzoylhydrazone; benzaldehyde
N-formylhydrazone; benzaldehyde N-benzoylhydrazone; naphthaldehyde
N-formylhydrazone; naphthaldehyde N-benzoylhydrazone; norbornanone
N-formylhydrazone; norbornanone N-benzoylhydrazone; camphor
N-formylhydrazone; camphor N-benzoylhydrazone; nopinone
N-formylhydrazone; nopinone N-benzoylhydrazone; 2-pyridinaldehyde
N-formylhydrazone; 2-pyridinalde hyde N-benzoylhydrazone;
salicylaldehyde N-formylhydrazone; salicylaldehyde
N-benzoylhydrazone; quinolinaldehyde N-formylhydrazone;
quinolinaldehyde N-benzoylhydrazone; furan-2-aldehyde
N-formylhydrazone; furan-2-aldehyde N-benzoylhydrazone;
naphthoquinone N-formylhydrazone; naphthoquinone
N-benzoylhydrazone; ionone N-formylhydrazone; ionone
N-benzoylhydrazone; lawsone N-formylhydrazone; and lawsone
N-benzoylhydrazone.
[0314] N--O Valence Stabilizer #27: Examples of carbazones
(diazenecarboxylic hydrazides), bis(carbazones), and
poly(carbazones) (N--O Bidentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diphenylcarbazone; 2-phenylcarbazone;
dinaphthylcarbazone; and 2-naphthylcarbazone.
[0315] N--O Valence Stabilizer #28: Examples of azo compounds with
hydroxyl or carboxy or carbonyl substitution at the ortho- (for
aryl) or alpha- or beta- (for alkyl) positions, Bis[o-(HO--) or
alpha- or beta-(HO--)azo compounds], or Poly[o-(HO--) or alpha- or
beta-(HO--)azo compounds) (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, or N--O Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-hydroxyazobenzene
[1-(phenylazo)-2-phenol]; 2,2'-dihydroxyazobenzene
(o,o'-dihydroxyazobenzene); (2-furan)azobenzene; Direct Blue 2B;
1-(4-nitrophenylazo)-2-naphthol; 1-(2-hydroxyphenylazo)-2-
-naphthol; 1-(2-methoxyphenyl azo)-2-naphthol;
pyridineazo-2-naphthol (PAN); pyridineazoresorcinol (PAR);
1-phenyl-4-(2-hydroxyphenylazo)-5-pyr- azolone;
1-phenyl-4-(2-methoxyphenylazo)-5-pyrazolone;
o-hydroxy-o'-(beta-aminoethylamino)azobenzene;
2-hydroxy-2'-methoxymethyl- eneoxyazobenzene; methyl red; turquoise
blue (reactive blue); sunset yellow; amaranth; tartrazine;
Eriochrome Black T; tropeolins; Allura Red; amaranth; Acid Alizarin
Violet N; Acid Blue 29; Acid Orange 8, 63, and 74; Acid Red 1, 4,
8, 37, 88, 97, 114, 151, and 183; Acid Violet 7; Acid Yellow 25,
29, 34, 42, 76, and 99; Brilliant Black BN; Brilliant Crocein;
Bordeaux R; Calcion; Chicago Sky Blue; Chromotrope; Cibacron
Brilliant Red; Cibacron Brilliant Yellow; Crocein Orange; Crystal
Scarlet; Calmagite; Direct Blue 71; Direct Red 23, 80, and 81;
Direct Violet 51; Direct Yellow 8 and 27; Fast Black; Flavazin;
Mordant Blue 9; Mordant Brown 1 and 33; Napthol Blue Black; New
Coccine; Nitrazine Yellow; Nitrosulfonazo III; Orange II; Orange G,
OT, and B; Ponceau 3R and SX; Polar Yellow; 2-oxazolylazobenzene;
and 2-benzoxazolylazobenzene.
[0316] N--O Valence Stabilizer #29: Examples of diazeneformamides,
diazeneacetamides, bis(diazenefonmamides), bis(diazeneacetamides),
poly(diazeneformamides), and poly(diazeneacetamides) (N--O
Bidentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazeneformamide, diazeneacetamide, phenyldiazeneformamide,
diphenyldiazeneformamide, phenyldiazeneacetamide, and
diphenyldiazeneacetamide.
[0317] N--O Valence Stabilizer #30: Examples of diazeneformic
acids, diazeneacetic acids, bis(diazeneformic acids),
bis(diazeneacetic acids), poly(diazeneformic acids),
poly(diazeneacetic acids) and derivatives thereof (N--O Bidentates,
N--O Tetradentates, N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diazeneformic acid,
diazeneacetic acid, phenyldiazeneformic acid, diphenyldiazeneformic
acid, phenyldiazeneacetic acid, and diphenyldiazeneacetic acid.
[0318] N--O Valence Stabilizer #31: Examples of
diazenefonmaldehydes, diazeneacetaldehydes,
bis(diazeneformaldehydes), bis(diazeneacetaldehydes- ),
poly(diazenefonmaldehydes), and poly(diazeneacctaldehydes) (N--O
Bidentates, N--O Tetradentates and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazenefonmaldehyde, diazeneacetaldehyde,
phenyldiazeneformaldehyde, diphenyldiazeneformaldehy- de,
phenyldiazeneacetaldehyde, and diphenyldiazeneacetaldehyde.
[0319] N--O Valence Stabilizer #32: Examples of
diazenediformamides, diazenediacetamides, bis(diazenediformamides),
bis(diazenediacetamides), poly(diazenedifonmamides), and
poly(diazenediacetamides) (N--O Tridentates and N--O Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazenedifonmamide, diazenediacetamide,
diphenydiazenediformamide, tetraphenyldiazenediformamide,
diphenyldiazenediacetamide, and tetraphenyldiazenediacetamide.
[0320] N--O Valence Stabilizer #33: Examples of diazenediformic
acids, diazenediacetic acids, bis(diazenediformic acids),
bis(diazenediacetic acids), poly(diazenediformic acids),
poly(diazenediacetic acids) and derivatives thereof (N--O
Tridentates and N--O Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diazenediformic acid,
diazenediacetic acid, phenyldiazenediformic acid,
diphenyldiazenediformic acid, phenyldiazenediacetic acid, and
diphenyldiazenediacetic acid.
[0321] N--O Valence Stabilizer #34: Examples of
diazenedifonmaldehydes, diazenediacetaldehydes,
bis(diazenediformaldehydes), bis(diazenediacetaldehydes),
poly(diazenedifonmaldehydes), and poly(diazenediacetaldehydes)
(N--O Tridentates and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+ include, but are not limited to: diazenedifonmaldehyde,
diazenediacetaldehyde, diphenyldiazenediformaldehy- de, and
diphenyldiazenediacetaldehyde.
[0322] N--O Valence Stabilizer #35: Examples of ortho-hydroxy (or
-carboxy) substituted formazans, bis(o-hydroxy or -carboxy
substituted formazans), and poly(o-hydroxy or carboxy substituted
formazans) (N--O Bidentates, N--O Tridentates, N--O Tetradentates,
and N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 1-(2-hydroxyphenyl)-3,5-diphenylformazan;
1-(2-methoxyphenyl)-3,5-dipheny- lformazan;
1,5-bis(2-hydroxyphenyl)-3-phenylformazan; and
5-bis(2-methoxyphenyl)-3-phenylformazan.
[0323] N--O Valence Stabilizer #36: Examples of ortho-hydroxy (or
-carboxy) substituted azines (including ketazines), bis(o-hydroxy
or carboxy substituted azines), and poly(o-hydroxy or carboxy
substituted azines) (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-hydroxy-1-benzalazine;
2-hydroxy-1-naphthalazine; and 2-hydroxy-1-cyclohexanonazine.
[0324] N--O Valence Stabilizer #37: Examples of Schiff Bases with
one Imine (C.dbd.N) Group and with ortho- or alpha-or beta-hydroxy
or carboxy or carbonyl substitution (N--O Bidentates, N--O
Tridentates, N--O Tetradentates, N--O Pentadentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: N-(Salicylaldehydo)isop- ropylamine;
N-(2-Furfuralo)isopropylamine; N-(2-Acetylfurano)isopropylamin- e;
N-(2-H ydroxyacetophenono)isopropylamine;
N-(Pyridoxalo)isopropylamine; N-(Salicylaldehydo)cyclohexylamine;
N-(2-Furfuralo)cyclohexylamine; N-(2-Acetyl furano)cyclohexylamine;
N-(2-Hydroxyacetophenono)cyclohexylam- ine;
N-(Pyridoxalo)cyclohexylamine; N-(Salicylaldehydo)aniline;
N-(2-Furfuralo)aniline (Stenhauz salt); N-(2-Acetylfurano)aniline;
N-(2-Hydroxyacetophenono)aniline; N-(Pyridoxalo)aniline;
N-(Salicylaldehydo)aminonorbornane; N-(2-Furfuralo)aminonorbornane;
N-(2-Acetylfurano)aminonorbornane;
N-(2-Hydroxyacetophenono)aminonorborna- ne;
N-(Pyridoxalo)aminonorbornane; (Salicylaldehydo)anisidine;
2-salicylideneiminobenzothiazole; (Salicylaldehydo)sulfamethazine;
and N'-histidine-3-methoxysalicylidenimine (V-his);
N-(o-carboxybenzaldehydo)- -2-aminophenol;
N-(salicylaldehydo)isatin; N-(2-furfuralo)isatin;
N-(2-acetylfurano)isatin; N-(pyridoxalo)isatin;
N-(2-hydroxyacetophenono)- isatin; hydrofuramide;
2-furancarboxaldehyde phenylhydrazone; 2-furancarboxaldehyde
2-pyridyl hydrazone; salicylaldehyde phenylhydrazone; and
salicylaldehyde 2-pyridyl hydrazone. Also includes hydrazones with
ortho-O substitution.
[0325] N--O Valence Stabilizer #38: Examples of Schiff Bases with
two Imine (C.dbd.N) Groups and with ortho- or alpha- or
beta-hydroxy or carboxy or carbonyl substitution (N--O Tridentates,
N--O Tetradentates, N--O Pentadentates, or N--O Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N'-(2,5-Furandicarboxaldehydo)diisopro- pylamine;
N,N'-(2,5-Furandicarboxaldehydo)dicyclohexylamine;
N,N'-(2,5-Furandicarboxaldehydo)dianiline;
N,N'-(2,5-Furandicarboxaldehyd- o)di-aminonorbornane;
N,N'-(o-Hydroxyphthalicdialdehydo)diisopropylamine;
N,N'-(o-Hydroxyphthalicdialdehydo)dicyclohexylamine;
N,N'-(o-Hydroxyphthalicdialdehydo)dianiline;
N,N'-(o-Hydroxyphthalicdiald- ehydo)di-aminonorbornane;
N,N'-(o-Hydroxyformylcamphoro)diisopropylamine;
N,N'-(o-Hydroxyformylcamphoro)dicyclohexylamine;
N,N'-(o-Hydroxyformylcam- phoro)dianiline;
N,N'-(o-Hydroxyformylcamphoro)di-aminonorbornane;
N,N'-(o-Hydroxydiacetylbenzeno)diisopropylamine;
N,N'-(o-Hydroxydiacetylb- enzeno)dicyclohexylamine;
N,N'-(o-Hydroxydiacetylbenzeno)dianiline;
N,N'-(o-Hydroxydiacetylbenzeno)di-aminonorbornane;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)diisopropylamine;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)dicyclohexylamine;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)dianiline;
N,N'-(3,6-Dihydroxy-1,2-- cyclohexanono)di-aminonorbornane;
N,N'-(2,5-Diacetyl furano)diisopropyl amine;
N,N'-(2,5-Diacetylfurano)dicyclohexylamine;
N,N'-(2,5-Diacetylfurano)dianiline;
N,N'-(2,5-Diacetylfurano)di-aminonorb- ornane;
N,N'-(Salicylaldehydo)ethylenediamine; N,N'-(o-Hydroxynaphthaldehy-
do)ethylenediamine; N,N'-(o-Hydroxyacetophenono)ethylenediamine;
N,N'-(Salicylaldehydo)trimethylenediamine;
N,N'-(o-Hydroxynaphthaldehydo)- trimethylenediamine;
N,N'-(o-Hydroxyacetophenono)trimethylenediamine;
N,N'-(Salicylaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Hydroxynapbthaldeh- ydo)cyclohexane-1,2-diamine;
N,N'-(o-Hydroxyacetophenono)cyclohexane-1,2-d- iamine;
N,N'-(Salicylaldehydo) 1,2-diaminobenzene; N,N'-(o-Hydroxynaphthal-
dehydo)-1,2-diaminobenzene;
N,N'-(o-Hydroxyacetophenono)-1,2-diaminobenzen- e;
N,N'-bis(salicylaldehydo)-1,12-diaminododecane (Saldn);
N,N'-bis(3-methoxysalicylaldehydo)-o-phenyldiamine;
N,N'-bis(3,4-difluorobenzaldehydo)-4,4'-benzidine; and
N,N'-phenylenebis(3-methoxysalicylidenimine) (V-ph-V). Also
includes hydrazones with ortho-O substitution.
[0326] N--O Valence Stabilizer #39: Examples of Schiff Bases with
three Imine (C.dbd.N) Groups and with ortho- or alpha- or
beta-hydroxy or carboxy or carbonyl substitution (N--O
Tetradentates, N--O Pentadentates, or N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N',N"-(Salicylaldehydo)tris(2-aminoethyl)amine;
N,N',N"-(o-Hydroxynaphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N"-(o-Hydroxyacetophenono)tris(2=aminoethyl)amine. Also
includes hydrazones with ortho-O substitution.
[0327] N--O Valence Stabilizer #40: Examples of silylaminoalcohols
(N--O Bidentates, N--O Tridentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: silatranes.
[0328] N--O Valence Stabilizer #41: Examples of hydroxyalkyl imines
(imino alcohols) (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-hydroxycyclohexylimine; 3-hydroxy-2-iminonorbornane;
2,2'-diiminodicyclohexyl ether; oxamide;
3-imino-1,5-pentanedialdehyde; iminodiacetic acid; and
iminodipropionic acid.
[0329] N--O Valence Stabilizer #42: Examples of hydroxyaryl amines
and hydroxyaryl imines (NO Bidentates, N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-aminophenol;
2-aminobenzoic acid (anthranilic acid); 2-aminoanisole;
o-phenetidine; o-anisidine; 2-hydroxymethyl)-alpha-aminot- oluene;
1-amino-2-naphthol; 2-amino-1-naphthol; 2,2'-di(aminomethyl)diphen-
ylketone; isophoronediamine; tris-2,4,6-dimethylaminomethyl phenol;
di(2-amino)phenyl ether; 1,3-di(2-amino)phenyl-2-hydroxypropane;
1,3-di(3-amino)phenyl-2-hydroxypropane;
1,3-di(2-hydroxy)phenyl-2-aminopr- opane;
1,3-di(3-hydroxy)phenyl-2-aminopropane;
2,2'-dihydroxyiminodibenzyl- ; 2,2'-iminodibenzoic acid;
2,2'-dihydroxyiminostilbene; poly(o-phenetidine);
poly(o-aminophenol); poly(o-anisidine); and
3-(anilino)propionamide.
[0330] N--O Valence Stabilizer #43: Examples of five-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional oxygen atom binding site not in a
ring (N--O Bidentates, N--O Tridentates, N--O Tetradentates, or
N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 2-hydroxypyrrole;
2-(methylhydroxy)methylpyrrole; 2,5-(hydroxymethyl)pyrrole;
2,5-(methylhydroxymethyl)pyrrol; imidazoline-2-one
(2-hydroxyimidazole); 2-hydroxythiazoline; 2-hydroxybenzimidazole;
2-hydroxybenzothiazole; 2-hydroxybenzoxazole; 2-hydantoin;
di-2-pyridylglyoxal (2,2'-pyridil); bis((1-pyrazolyl)methane)ether;
bis(2-(1-pyrazolyl)ethane)ether; bis(benzimidazolylmethane)ether;
bis(benzimidazolylethane)ether; tris(imidazolyl)methanol;
tris(imidazolylmethane)methanol;
N-hydroxymethyl-N,N-(benzimidazolylmethane)amine;
N-(2-hydroxyethyl)-N,N-- (benzimidazolylmethane)amine;
N,N'-di(benzimidazolylmethane)-1,3-diamino-2- -hydroxypropane;
N,N,N',N'-tetrakis(benzimidazolylmethane)-1,3-diamino-2-h-
ydroxypropane; bis(N,N-((4-imidazolyl)methane)2-aminoethane)ether;
4-carboxybenzotriazole; antipyrine; 4-aminoantipyrine (aap);
hydantoin; aminoalkylhydantoins; 2,5-oxazolidinedione;
benzyldibenzoyltriazole (bdbt); 5-hydroxymethylimidazole;
dicarboxyalkylbenzotriazoles; bis(hydroxyphenyl)aminotriazoles;
pyrrole-2-carboxaldehyde; (oxopyrrolidinylalkyl)triazoles;
alkoxybenzotriazoles; aryloxybenzotriazoles;
3-salicylamido-4,5-dihydro-1,2,4-triazole; 5-(alkoxy)benzotriazole;
(polyoxyalkylene)oxazolidines;
1-(dialkylaminomethyl)-5-carboxyalkylbenzotriazole;
1-(2-hydroxyethyl)imidazoline; 1-acetoxyimidazole;
1-acetylimidazole; benzotriazolecarboxylic acid;
poly(oxyalkylated)pyrazoles; poly(oxyalkylated)thiadiazoles;
1,2,4-triazole-3-carboxylic acid; 5-hydroxypyrazole;
3-phenyl-1,2,4-triazol-5-one (ptr); 1-acetylbenzimidazole;
1-[(acetoxy)ethyl]benzimidazole; creatinine; indole-2-carboxylic
acid; pyrrole-2-carboxylic acid; imidazole-2-carboxylic acid;
pyrazole-2-carboxylic acid; and 1,1'-oxalyldiimidazole.
[0331] N--O Valence Stabilizer #44: Examples of six-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional oxygen atom binding site not in a
ring (N--O Bidentates, N--O Tridentates, N--O Tetradentates, or
N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 4-aminomethyl-3-pyridin- emethanol
(including pyridoxamine); 2-hydroxypyridine;
2-(methylhydroxy)methylpyridine;
2-(2-(methylhydroxy)ethyl)pyridine; 2,6-(hydroxymethyl)pyridine;
2,6-(methylhydroxymethyl)pyridine; 2-hydroxypyrimidine;
2-dihydroxymethylpyrimidine; 2-hydroxyquinoline; 8-hydroxyquinoline
(oxine); 8-methylhydroxyquinoline; 2-hydroxyquinazoline; orotic
acid (1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimid- inecarboxylic acid)
(6-uracilcarboxylic acid); 1-methylpyrimidine-2-one; uracil;
6-hydroxypurine; bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminomet-
hane)ether;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminoetbane)ether;
quinazol-4-one; quinazol-2-one; 5-azathymine;
2-hydroxybenzimidazole (2-hbz); guanine; 1,3,5-triazin-6-one;
6-hydroxy-1,3,5-triazine; 4,6-dihydroxy-1,3,5-triazine; triazine
carboxylic acids; 2,3-dihydroxypyridine; thiomorpholin-3-one;
hydroxytetrahydropyrimidines; 2-piperazinones; 2-piperidinones;
dilituric acid; actinoquinol; caffeine; citrazinic acid; picolinic
acid; 2-quinolol; 2,6-dimethoxypyridine; quinoxaline-2-carboxylic
acid; flucytosine; hypoxanthine; hexamethylolmelamine; hydroorotic
acid; isoorotic acid; xantbine; leucopterin; nitroorotic acid;
8-azaguanine; and cyanuric acid.
[0332] N--O Valence Stabilizer #45: Examples of five-membered
heterocyclic rings containing one or two oxygen atoms at least one
additional nitrogen atom binding site not in a ring (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-aminofuran; 2,5-diaminofuran; 2-aminomethylfuran;
2,5-di(aminomethyl)furan; 2-aminobenzofuran; and
2-amino-1,3-dioxolane.
[0333] N--O Valence Stabilizer #46: Examples of six-membered
heterocyclic rings containing one or two oxygen atoms at least one
additional nitrogen atom binding site not in a ring (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-aminopyran; 2,6-diaminopyran; 2-aminomethylpyran;
2,6-di(aminomethyl)pyran; and 2-aminobenzopyran.
[0334] N--O Valence Stabilizer #47: Examples of five-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional oxygen atom binding site in a
separate ring (N--O Bidentates, N--O Tridentates, N--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-(2-furan)pyrrole; 2,5-di(2-furan)pyrrole;
2-(2-pyran)pyrrole; 2,5-di(2-pyran)pyrrole; 2,5-di(2-pyrrole)furan;
and 2,6-di(2-pyrrole)pyran.
[0335] N--O Valence Stabilizer #48: Examples of six-membered
heterocyclic rings containing one, two, three, or four nitrogen
atoms at least one additional oxygen atom binding site in a
separate ring (N--O Bidentates, N--O Tridentates, N--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-(2-furan)pyridine; 2,6-di(2-furan)pyridine;
2-(2-pyran)pyridine; 2,6-di(2-pyran)pyridine;
2,5-di(2-pyridyl)furan; 2,6-di(2-pyridyl)pyran; and
drometrizole.
[0336] N--O Valence Stabilizer #49: Examples of two-, three-,
four-, six-, eight-, and ten-membered macrocyclics, macrobicyclics,
and macropolycyclics (including catapinands, cryptands, cyclidenes,
and sepulchrates) wherein all binding sites are composed of
nitrogen (usually amine or imine groups) or oxygen (usually
hydroxy, carboxy, or carbonyl groups) and are not contained in
component heterocyclic rings (N--O Bidentates, N-O Tridentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
azaoxacyclobutane ([4]aneNO); azaoxacyclopentane ([5]aneNO);
azaoxacyclohexane ([6]aneNO); azaoxacycloheptane ([7]aneNO);
azaoxacyclooctane ([8]aneNO); azaoxacyclobutene ([4]eneNO);
azaoxacyclopentene ([5]eneNO); azaoxacyclohexene ([6]eneNO);
azaoxacycloheptene ([7]eneNO); azaoxacyclooctene ([8]eneNO);
azaoxacyclobutadiene ([4]dieneNO); azaoxacyclopentadiene
([5]dieneNO); azaoxacyclohexadiene ([6]dieneNO);
azaoxacycloheptadiene ([7]dieneNO); azaoxacyclooctadiene
([8]dieneNO); diazaoxacyclohexane ([6]aneON.sub.2);
diazaoxacycloheptane ([7]aneON.sub.2); diazaoxacyclooctane
([8]aneON.sub.2); diazaoxacyclononane ([9]aneON.sub.2);
diazaoxacyclodecane ([10]aneON.sub.2); diazaoxacycloundecane
([11]aneON.sub.2); diazaoxacyclododecane ([12]aneON.sub.2);
diazaoxacyclohexene ([6]eneON.sub.2); diazaoxacycloheptene
([7]eneON.sub.2); diazaoxacyclooctene ([8]eneON.sub.2);
diazaoxacyclononene ([9]eneON.sub.2); diazaoxacyclodecene
([10]eneON.sub.2); diazaoxacycloundecene ([11]eneON.sub.2);
diazaoxacyclododecene ([12]eneON.sub.2); diazadioxacyclooctane
([8]aneO.sub.2N.sub.2); diazadioxacyclononane
([9]aneO.sub.2N.sub.2); diazadioxacyclodecane
([10]aneO.sub.2N.sub.2); diazadioxacycloundecane
([11]aneO.sub.2N.sub.2); diazadioxacyclododecane
([12]aneO.sub.2N.sub.2); diazadioxacyclotridecane
([13]aneO.sub.2N.sub.2); diazadioxacyclotetradec- ane
([14]aneO.sub.2N.sub.2); diazadioxacyclopentadecane
([15]aneO.sub.2N.sub.2); diazadioxacyclohexadecane
([16]aneO.sub.2N.sub.2); diazadioxacycloheptadecane
([17]aneO.sub.2N.sub.2); diazadioxacyclooctadecane
([18]aneO.sub.2N.sub.2); diazadioxacyclononadecane
([19]aneON.sub.2); diazadioxacycloeicosane ([20]aneO.sub.2N.sub.2);
diazadioxacyclooctadiene ([8]dieneO.sub.2N.sub.2);
diazadioxacyclononadiene ([9]dieneO.sub.2N.sub.2);
diazadioxacyclodecadiene ([10]dieneO.sub.2N.sub.2);
diazadioxacycloundecadiene ([11]dieneO.sub.2N.sub.2);
diazadioxacyclododecadiene ([12]dieneO.sub.2N.sub.2);
diazadioxacyclotridecadiene ([13]dieneO.sub.2N.sub.2);
diazadioxacyclotetradecadiene ([14]dieneO.sub.2N.sub.2);
diazadioxacyclopentadecadiene ([15]dieneO.sub.2N.sub.2);
diazadioxacyclohexadecadiene ([16]dieneO.sub.2N.sub.2);
diazadioxacycloheptadecadiene ([17]dieneO.sub.2N.sub.2);
diazadioxacyclooctadecadiene ([18]dieneO.sub.2N.sub.2);
diazadioxacyclononadecadiene ([19]dieneO.sub.2N.sub.2); and
diazadioxacycloeicosadiene ([20]dieneO.sub.2N.sub.2).
[0337] N--O Valence Stabilizer #50: Examples of four-, six-,
eight-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen or
oxygen and are contained in component heterocyclic rings (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dipyrandipyridines; difurandipyrroles;
tripyrantripyridines; trifurantripyrroles;
tetrapyrantetrapyridines; and tetrafurantetrapyrroles.
[0338] N--O Valence Stabilizer #51: Examples of four-, six-,
eight-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen or
oxygen and are contained in a combination of heterocyclic rings and
amine, imine, hydroxy, carboxy, or carbonyl groups (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: azaoxatetraphyrins; diazadioxatetraphyrins;
azaoxahexaphyrins; diazadioxahexaphyrins; and
triazatrioxahexaphyrins.
[0339] S--O Valence Stabilizer #1: Examples of 1,3-monothioketones
(monothio-beta-ketonates), 1,3,5-monothioketones,
1,3,5-dithioketones, bis(1,3-monothioketones), and
poly(1,3-monothioketones) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hexafluoropenta-2-thione-4-ketone;
1,3-diphenyl-1,3-propana-1-thione-3-ketone; benzoylthiopinacolone;
cyclohexoylthiocyclohexoylmethane; diphenylpentanedithionate;
tetramethylnonanedithionate; hexafluoroheptanedithionate;
trifluoroheptanedithionate; 1-(2-thienyl)-butan-1-thione-3-ketone,
1-(2-naphthyl)-butan-1-thione-3-ketone, and
trifluoroacetylthiocamphor.
[0340] S--O Valence Stabilizer #2: Examples of thiomalonamides
(thiomalonodiamides), bis(thiomalonamides), and polythiomalonamides
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiomalonamide, N-phenylthiomalonamide, N-benzylthiomalonamide,
N-pentafluorophenylthioma- lonamide, N-cyclohexylthiomalonamide,
N-norbornylthiomalonamide, N,N'-diphenylthiomalonamide,
N,N'-dibenzylthiomalonamide,
N,N'-dipentafluorophenylthiomalonamide,
N,N'-dicyclohexylthiomalonamide, and
N,N'-norbornylthiomalonamide.
[0341] S--O Valence Stabilizer #3: Examples of
2-thioacylacetamides, 2-acylthioacetamides,
bis(2-thioacylacetamides), bis(2acylthioacetamides)- ,
poly(2-thioacylacetamides), and poly(2-Acylthioacetamides) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2-acetothioacetamide, 2-thioacetoacetamide,
N-phenyl-2-acetothioacetamide,
N-pentafluorophenyl-2-acetothioacetamide,
N-benzyl-2-acetothioacetamide, N-cyclohexyl-2-acetothioacetamide,
N-norbornyl-2-acetothioacetamide, N-phenyl-2-benzothioacetamide,
N-pentafluorophenyl-2-pentafluorobenzothio- acetamide, and
N-cyclohexyl-2-cyclohexothioacetamide.
[0342] S--O Valence Stabilizer #4: Examples of dithiodicarbonic
diamides, bis(dithiodicarbonic diamides), and poly(dithiodicarbonic
diamides) (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: dithiodicarbonic diamide; N-phenyldithiodicarbonic
diamide; N-pentafluorophenyldithiodicar- bonic diamide;
N-benzyldithiodicarbonic diamide; N-cyclohexyldithiodicarbo- nic
diamide; N-norbornyldithiodicarbonic diamide;
N,N'-diphenyldithiodicar- bonic diamide;
N,N'-dipentafluorophenyldithiodicarbonic diamide;
N,N'-dibenzyldithiodicarbonic diamide;
N,N'-dicyclohexyldithiodicarbonic diamide; and
N,N'-dinorbornyldithiodicarbonic diamide.
[0343] S--O Valence Stabilizer #5: Examples of
monothiohypophosphoric acids, bis(monothiohypophosphoric acids),
poly(monothiohypophosphoric acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
monothiohypophosphoric acid, methylmonothiohypophosphoric acid,
isopropylmonothiohypophosphoric acid,
tert-butylmonothiohypophosphoric acid, phenylmonothiohypophosphoric
acid, pentafluorophenylmonothiohypopho- sphoric acid,
benzylmonothiohypophosphoric acid, cyclohexylmonothiohypopho-
sphoric acid, norbornylmonothiohypophosphoric acid,
dimethylmonothiohypophosphoric acid,
diisopropylmonothiohypophosphoric acid,
di-tert-butylmonothiohypophosphoric acid,
diphenylmonothiohypophosp- horic acid,
di-pentafluorophenylmonothiohypophosphoric acid,
dibenzylmonothiohypophosphoric acid,
dicyclohexylmonothiohypophosphoric acid, and
dinorbornylmonothiohypophosphoric acid.
[0344] S--O Valence Stabilizer #6: Examples of
monothiohypophosphoramides, bis(monothiohypophosphoramides), and
poly(monothiohypophosphoramides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: monothiohypophosphorami- de,
N-methylmonothiohypophosphoramide,
N-isopropylmonothiohypophosphoramid- e,
N-tert-butylmonothiohypophosphoramide,
N-phenylmonothiohypophosphoramid- e,
N-pentafluorophenylmonothiohypophosphoramide,
N-benzylmonothiohypophosp- horamide,
N-cyclohexylmonothiohypophosphoramide, N-norbornylmonothiohypoph-
osphoramide, N,N'"-dimethylmonothiohypophosphoramide,
N,N'"-diisopropylmonothiohypophosphoramide,
N,N'"-di-tert-butylmonothiohy- pophosphoramide,
N,N'"-diphenylmonothiohypophosphoramide,
N,N'"-di-pentafluorophenylmonothiohypophosphoramide,
N,N'"-dibenzylmonothiohypophosphoramide,
N,N'"-dicyclohexylmonothiohypoph- osphoramide, and
N,N"-dinorbornylmonothiohypophosphoramide.
[0345] S--O Valence Stabilizer #7: Examples of
monothioimidodiphosphoric acids, monothiohydrazidodiphosphoric
acids, bis(monothioimidodiphosphoric acids),
bis(monothiohydrazidodiphosphoric acids), poly(monothioimidodipho-
sphoric acids), poly(monothiohydrazidodiphosphoric acids), and
derivatives thereof (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: monothioimidodiphosphor- ic acid,
methylmonothioimidodiphosphoric acid, isopropylmonothioimidodipho-
sphoric acid, tert-butylnonothioimidodiphosphoric acid,
phenylmonothioimidodiphosphoric acid,
pentafluorophenylmonothioimidodipho- sphoric acid,
benzylmonothioimidodiphosphoric acid,
cyclohexylmonothioimidodiphosphoric acid,
norbornylmonothioimidodiphospho- ric acid,
dimethylmonothioimidodiphosphoric acid, diisopropylmonothioimido-
diphosphoric acid, di-tert-butylmonothioimidodiphosphoric acid,
diphenylmonothioimidodiphosphoric acid,
di-pentafluorophenylmonothioimido- diphosphoric acid,
dibenzylmonothioimidodiphosphoric acid,
dicyclohexylmonothioimidodiphosphoric acid, and
dinorbornylmonothioimidod- iphosphoric acid.
[0346] S--O Valence Stabilizer #8: Examples of
monothioimidodiphosphoramid- es, monothiohydrazidodiphosphoramides,
bis(monothioimidodiphosphoramides),
bis(monothiohydrazidodiphosphoramides),
poly(monothioimidodiphosphoramide- s), and
poly(monothiohydrazidodiphosphoramides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: monothioimidodiphosphoramide,
N-methylmonothioimidodiphosphoramide,
N-isopropylmonothioimidodiphosphora- mide,
N-tert-butylmonothioimidodiphosphoramide,
N-phenylmonothioimidodipho- sphoramide,
N-pentafluorophenylmonothioimidodiphosphoramide,
N-benzylmonothioimidodiphosphoramide,
N-cyclohexylmonothioimidodiphosphor- amide,
N-norbornylmonothioimidodiphosphoramide,
N,N'"-dimethylmonothioimid- odiphosphoramide,
N,N'"-diisopropylmonothioimidodiphosphoramide,
N,N'"-di-tert-butylmonothioimidodiphosphoramide,
N,N'"-diphenylmonothioim- idodiphosphoramide,
N,N'"-di-pentafluorophenylmonothioimidodiphosphoramide- ,
N,N'"-dibenzylmonothioimidodiphosphoramide,
N,N'"-dicyclohexylmonothioim- idodiphosphoramide, and
N,N'"-dinorbornylmonothioimidodiphosphoramide.
[0347] S--O Valence Stabilizer #9: Examples of
monothiodiphosphoramides, bis(monothiodiphosphoramides), and
poly(monothiodiphosphoramides) (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: monothiodiphosphoramide- ,
N-methylmonothiodipbosphoramide,
N-isopropylmonothiodiphosphoramide,
N-tert-butylmonothiodiphosphoramide,
N-phenylmonothiodiphosphoramide,
N-pentafluorophenylmonothiodiphosphoramide,
N-benzylmonothiodiphosphorami- de,
N-cyclohexylmonothiodiphosphoramide,
N-norbornylmonothiodiphosphoramid- e,
N,N'"-dimethylmonothiodiphosphoramide,
N,N'"-diisopropylmonotbiodiphosp- horamide,
N,N'"-di-tert-butylmonothiodiphosphoramide,
N,N'"-diphenylmonothiodiphosphoramide,
N,N'"-di-pentafluorophenylmonothio- diphosphoramide,
N,N'"-dibenzylmonothiodiphosphoramide,
N,N'"-dicyclohexylmonothiodiphosphoramide, and
N,N'"-dinorbornylmonothiod- iphosphoramide.
[0348] S--O Valence Stabilizer #10: Examples of
monothiodiphosphoric acids, bis(monotbiodiphosphoric acids),
poly(monothiodiphosphoric acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
monothiodiphosphoric acid, methylmonothiodiphosphoric acid,
isopropylmonothiodiphosphoric acid, tert-butylmonothiodiphosphoric
acid, phenylmonothiodiphosphoric acid,
pentafluorophenylmonothiodiphosphoric acid,
benzylmonothiodiphosphoric acid, cyclohexylmonothiodiphosphoric
acid, norbornylmonothiodiphosphoric acid,
dimethylmonothiodiphosphoric acid, diisopropylmonothiodiphosphoric
acid, di-tert-butylmonothiodiphosph- oric acid,
diphenylmonothiodiphosphoric acid, di-pentafluorophenylmonothio-
diphosphoric acid, dibenzylmonothiodiphosphoric acid,
dicyclohexylmonothiodiphospboric acid, and
dinorbornylmonothiodiphosphori- c acid.
[0349] S--O Valence Stabilizer #11: Examples of monothiocarbamates,
bis(monothiocarbamates), and poly(monothiocarbamates) (including
N-hydroxymonothiocarbamates and N-mercaptomonothiocarbamates) (S--O
Bidentates, S--O Tridentates, and S--O Tetradentates) that rmeet
the requirements for use as "wide band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dimethylmonothiocarbama- te (dmmtc);
di(trifluorodimethyl)monothiocarbamate; diethylmonothiocarbamate
(demtc); dipropylmonothiocarbamate; diisopropylmonothiocarbamate;
dibutylmonothiocarbamate; ditertbutylmonothiocarbamate;
dicyanamidomonothiocarbamate; diphenylmonothiocarbamate;
di(pentafluorophenyl)monothiocarbamate; dibenzylmonothiocarbamate;
dinaphthylmonothiocarbamate; dicyclohexylmonothiocarbamate;
dinorbornylmonothiocarbamate; diadamantylmonothiocarbamate;
pyrrolidinomonothiocarbamate (pyrmtc); piperidinomonothiocarbamate
(pipmtc); morpholinomonothiocarbamate (mormtc);
thiamorpholinomonothiocarbamate; 3-pyrrolinomonothiocarbamate;
pyrrolomonothiocarbamate; oxazolomonothiocarbamate;
isoxazolomonothiocarbamate; thiazolomonothiocarbamate;
isothiazolomonothiocarbamate; indolomonothiocarbamate;
carbazolomonothiocarbamate; pyrazolinomonothiocarbamate;
imidazolinomonothiocarbamate; pyrazolomonothiocarbamate;
imidazolomonothiocarbamate; indazolomonothiocarbamate; and
triazolomonothiocarbamate.
[0350] Miscellaneous Valence Stabilizer #1: Examples of hydroxo and
oxo functionalities that meet the requirements for use as "wide
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: water (H.sub.2O); dioxygen (O.sub.2); oxide
(O.sup.2.sup.-); hydroxide (OH.sup.-); peroxo groups
(O.sub.2.sup.2-); and superoxo groups (O.sub.2.sup.-).
[0351] As with the inorganic valence stabilizers, crosses between
two or more organic stabilizers can be used. For example, in some
instances it may be desirable to form a valence stabilizer out of a
nitrogen-containing heterocyclic and an amine ligand. During the
synthesis process, both of these materials will complex with the
MnIII or MnIV ion to produce a mixed nitrogen heterocyclic/amine
valence stabilizer compound from the pigment solution.
[0352] 3c) Narrow Band Inorganic Valence Stabilizers
[0353] Additional valence stabilizers can be used in conjunction
with the MnIII and MnIV ions for corrosion protection. However,
these less typical stabilizers suffer from disadvantages that make
their selection over the previously mentioned wide band valence
stabilizers less desirable. For this reason, we term them "narrow
band" valence stabilizers because of their limited applications.
Narrow band stabilizers exhibit some limitation in their use when
compared to wide band stabilizers. Narrow band inorganic
stabilizers may be toxic or may complex MnII or MnIV only with
difficulty. These narrow band stabilizers include, but are not
limited to, bismuthates, gennanates, arsenates, and carbonates. For
example, valence stabilizers using arsenate are less desirable
because their inherent toxicity is very large (greater than PbIV or
CrVI), although they may be very effective at inhibiting corrosion
when used with MnII. Arsenates could be used as MnIII valence
stabilizers in situations where the toxicity of the pigment is not
a factor in its use.
[0354] Modifications of wide band inorganic valence stabilizers can
result in a complex with reduced corrosion inhibition. The central
cavity of the heteropolymetallates can contain ions in addition to
the desired MnIII or MnIV ion. For example, the use of
silicomolybdates, phosphomolybdates, silicotungstates, and
phosphotungstates is possible. In these MnIII- or MnIV-valence
stabilizer complexes, Si.sup.+4 or P.sup.+5 ions also occupy the
central cavity of the complex with the MnIII or MnIV ion. The
inclusion of additional ions in the central cavity reduces the
stability of the complex, and thereby leads to lower corrosion
protection. Nonetheless, these complexes also demonstrate some
corrosion inhibiting activity. The additional ions that can be
included within the central cavity of the heteropolymetallates
described above depend upon the size of the central cavity, which
in turn depends upon the specific chemistry exhibited by an
inorganic valence stabilizer (e.g., molybdate, tungstate,
periodate, etc.) In general, these additional ions must also be
small so as to ensure the stability of the formed MnIII- or
MnIV-valence stabilized complex. Examples of small additional ions
include, but are not limited to: B.sup.+3, Al.sup.+3, Si.sup.+4,
P.sup.+5, Ti.sup.+4, V.sup.+5, V.sup.+4, Cr.sup.+6, Cr.sup.+3,
Mn.sup.+2, Fe.sup.+3, Fe.sup.+2, CO.sup.+3, CO.sup.+2, Ni.sup.+2,
N.sup.+3, Ni.sup.+4, CU.sup.+2, Cu.sup.+3, Zn.sup.+2, Ga.sup.+3,
Ge.sup.+4, AS.sup.+5, As.sup.+3, Zr.sup.+4, and Ce.sup.+4.
[0355] Water-soluble precursors for these materials are desirable.
Typically, the free acids (e.g., silicomolybdic acid,
phosphotungstic acid, borotungstic acid, etc.) offer the most
water-soluble precursors for these materials.
[0356] 3d) Narrow Band Organic Valence Stabilizers
[0357] Narrow band organic valence:stabilizers include those
general classes of chemical compounds that result in MnIII- or
MnIV-valence stabilizer compounds that are either less stable, more
soluble in water, or more toxic than the wide band organic
stabilizers.
6TABLE 5 Narrow Band Organic Valence Stabilizers for the Mn.sup.+3
and Mn.sup.+4 Ions General Structural Name (Type of Organic)
Structural Representation N Valence Stabilizer #1: Macrocyclic
ligands containing five, seven, or Five-, Seven-, or Nine-Membered
nine nitrogen binding sites to valence stabilize Macrocyclics,
Macrobicyclics, and the central metal ion. Can include other
Macropolycyclics (including Catapinands, hydrocarbon or ring
systems bound to this Cryptands, Cyclidenes, and Sepulchrates)
macrocyclic ligand, but they do not coordinate wherein all Binding
Sites are composed of with the stabilized, high valence metal ion.
This Nitrogen (usually amine or imine groups) ligand and/or
attached, uncoordinating and are not contained in Component
hydrocarbons/rings may or may not have Heterocyclic Rings (N--N
Tridentates, N--N halogen or polarizing or water- Tetradentates,
and N--N Hexadentates) insolubilizing/solubilizing groups attached.
N Valence Stabilizer #2: Macrocyclic ligands containing a total of
five or Five-, or Seven-Membered Macrocyclics, seven five-membered
heterocyclic rings Macrobicyclics, and Macropolycyclics containing
nitrogen binding sites. Can include (including Catapinands,
Cryptands, other hydrocarbon/ring systems bound to this Cyclidenes,
and Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Nitrogen with the
stabilized, high valence metal ion. This and are contained in
Component 5- ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (N--N hydrocarbon/rings may or may not have
halogen Tridentates, N--N Tetradentates, or N--N or polarizing or
water-insolubilizing groups Hexadentates) attached. N Valence
Stabilizer #3: Macrocyclic ligands containing at least one 5-
Five-, Seven-, or Nine-Membered membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and heterocyclic rings provide
nitrogen binding sites Macropolycyclics (including Catapinands, to
valence stabilize the central metal ion. Other Cryptands,
Cyclidenes, and Sepulchrates) amine or imine binding sites can also
be wherein all Binding Sites are composed of included in the
macrocyclic ligand, so long as Nitrogen and are contained in a the
total number of binding sites is five, seven, Combination of
5-Membered Heterocyclic or nine. Can include other hydrocarbon/ring
Rings and Amine or Imine Groups (N--N systems bound to this
macrocyclic ligand, but Tridentates, N--N Tetradentates, or N--N
they do not coordinate with the stabilized, high Hexadentates)
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. N Valence Stabilizer #4:
Macrocyclic ligands containing a total of five or Five- or
Seven-Membered Macrocyclics, seven six-membered heterocyclic rings
Macrobicyclics, and Macropolycyclics containing nitrogen binding
sites. Can include (including Catapinands, Cryptands, other
hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Nitrogen with the
stabilized, high valence metal ion. This and are contained in
Component 6- ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (N--N hydrocarbon/rings may or may not have
halogen Tridentates, N--N Tetradentates, or N--N or polarizing or
water-insolubilizing groups Hexadentates) attached. N Valence
Stabilizer #5: Macrocyclic ligands containing at least one 6-
Five-, Seven-, or Nine-Membered membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and heterocyclic rings provide
nitrogen binding sites Macropolycyclics (including Catapinands, to
valence stabilize the central metal ion. Other Cryptands,
Cyclidenes, and Sepulchrates) amine or imine binding sites can also
be wherein all Binding Sites are composed of included in the
macrocyclic ligand, so long as Nitrogen and are contained in a the
total number of binding sites is five, seven, Combination of
6-Membered Heterocyclic or nine. Can include other hydrocarbon/ring
Rings and Amine or Imine Groups (N--N systems bound to this
macrocyclic ligand, but Tridentates, N--N Tetradentates, or N--N
they do not coordinate with the stabilized, high Hexadentates)
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. N Valence Stabilizer #6:
N(SiR.sub.3).sub.3, R'N(SiR.sub.3).sub.2, or R'R"N(SiR.sub.3) for
Silylamines and Silazanes, including silylamines; and
[RR"Si--NR'].sub.x (x = 1-10) for Macrocyclic Derivatives, wherein
at least silazanes where R, R', and R" represents H or one Nitrogen
Atom is a Binding Site (N any organic functional group wherein the
Monodentates, N--N Bidentates, N--N number of carbon atoms ranges
from 0 to 35, Tridentates, N--N Tetradentates, and N--N optionally
having halogen or polarizing or Hexadentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. N Valence
Stabilizer #7: RR'--N--C(.dbd.NH)NR"R"', where R, R', R", and
Guanidines, Diguanidines, and R"' represent H or any organic
functional group Polyguanidines (N--N Bidentates, N--N wherein the
number of carbon atoms ranges Tridentates, N--N Tetradentates, and
N--N from 0 to 40, optionally having halogen or Hexadentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #8: RR'--N--P(.dbd.N)--N--R"R"', where R, R', R", and
Phosphonitrile Amides, and R"' represent H or any organic
functional group Bis(phosphonitrile amides) (N--N wherein the
number of carbon atoms ranges Bidentates, N--N Tetradentates) from
0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #9:
(NH.dbd.)PR""(--NRR')(--NR"R"'), where R, R', Phosphonimidic
Diamides, R", R"', and R"" represent H or any organic
Bis(Phosphonimidic Diamides), and functional group wherein the
number of carbon Poly(Phosphonimidic Diamides) (N--N atoms ranges
from 0 to 40, optionally having Bidentates, N--N Tetradentates)
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #10: (NH.dbd.)PR"'(--NRR')(--OR") for
Phosphonamidimidic Acid, phosphonamidimidic acid and
(NH.dbd.)PR"'(-- Phosphonamidimidothioic Acid, NRR')(--SR") for
phosphonamidimidothioic Bis(Phosphonamidimidic Acid), acid, where
R, R', R", and R"' represent H or Bis(Phosphonamidimidothioic
Acid), any organic functional group wherein the
Poly(Phosphonamidimidic Acid), number of carbon atoms ranges from 0
to 40, Poly(Phosphonamidimidothioic Acid), and optionally having
halogen or polarizing or derivatives thereof (N--N Bidentates, and
N-- water-insolubilizing/solubilizing groups N Tetradentates)
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #11: C.sub.5H.sub.5N--CR.dbd.NR', where
C.sub.5H.sub.5N is a pyridine Pyridinaldimines,
Bis(pyridinaldimines), derivative, R is typically an aromatic
constituent and Poly(pyridinaldimines) (N--N (i.e.
--C.sub.6H.sub.5), and R' represents H or any organic Bidentates,
N--N Tridentates, and N--N functional group wherein the number of
carbon Tetradentates) atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #12: R--NH--N.dbd.R', where R and R' represent H
or Hydrazones, Bis(hydrazones), and any organic functional group
wherein the Poly(hydrazones) (N Monodentates, N--N number of carbon
atoms ranges from 0 to 40, Bidentates, N--N Tridentates, and N--N
optionally having halogen or polarizing or Tetradentates)
water-insolubilizing/solubilizing groups attached. (Either R or R'
is typically an aryl group.) Ligand can also contain nonbinding N,
O, S, or P atoms. N Valence Stabilizer #13: R--N.dbd.N--R' for azo
compounds, R--N.dbd.N--NH--R' Azo compounds including triazenes
without for triazenes, where R, and R' represent H or chelate
substitution at the ortho- (for aryl) any organic functional group
wherein the or alpha- or beta- (for alkyl) positions, number of
carbon atoms ranges from 0 to 40, Bis(azo compounds), or Poly(azo
optionally having halogen or polarizing or compounds) (N
Monodentates, N--N water-insolubilizing/solubilizing groups
Bidentates, or N--N--N Tridentates) attached. (Not including ortho-
chelate substituted aryl azo compounds, and alpha- or
beta-substituted alkyl azo compounds.) Ligand can also contain
nonbinding N, O, S, or P atoms. N Valence Stabilizer #14:
R--N.dbd.N--CR'.dbd.N--NR"R"', where R, R', R", and Formazans,
Bis(formazans), and R"' represent H, or any organic-functional
Poly(formazans) without ortho- hydroxy, group wherein the number of
carbon atoms carboxy, thiol, mercapto, amino, or ranges from 0 to
40, optionally having halogen hydrazido substitution (N--N
Bidentates, N-- or polarizing or water- N Tetradentates, and N--N
Hexadentates) insolubilizing/solubilizing groups attached. (Not
including ortho- hydroxy, carboxy, thiol, mercapto, amino, or
hydrazido substitution.) Ligand can also contain nonbinding N, O,
S, or P atoms. N Valence Stabilizer #15:
R--CH.dbd.N--CHR'--N.dbd.CHR", where R, R', and R" Hydramides (N--N
Bidentates) represent H, or any organic functional group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. (R, R', and R" are typically aryl derivatives.) Ligand
can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #16: RR'C.dbd.N--N.dbd.CR"R"' or RR'C.dbd.N--NR"R"' (for
Azines (including ketazines), Bis(azines), ketazines), where R, R',
R", and R"' represent and Poly(azines) without ortho- hydroxy, H,
or any organic functional group wherein the carboxy, thiol,
mercapto, amino, or number of carbon atoms ranges from 0 to 40,
hydrazido substitution (N--N Bidentates, N-- optionally having
halogen or polarizing or N Tetradentates, and N--N Hexadentates)
water-insolubilizing/solubilizing groups attached. (Not including
ortho- hydroxy, carboxy, thiol, mercapto, amino, or hydrazido
substitution.) Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #17: RR'C.dbd.N--R", where R, R', and
R" represent H, Schiff Bases with one Imine (C.dbd.N) Group or any
organic functional group wherein the and without ortho- (for aryl
constituents) or number of carbon atoms ranges from 0 to 40, alpha-
or beta- (for alkyl constituents) optionally having halogen or
polarizing or hydroxy, carboxy, carbonyl, thiol,
water-insolubilizing/solubilizing groups mercapto, thiocarbonyl,
amino, imino, attached. (Not including ortho-, alpha-, or beta-
oximo, diazeno, or hydrazido substitution hydroxy, carboxy,
carbonyl, thiol, mercapto, (N Monodentates) thiocarbonyl, amino,
imino, oximo, diazeno, or hydrazido substitution.) Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #18:
Isocyanides, cyanamides, and related ligands Isocyanide and
Cyanamide and related where the nitrogen atom is directly complexed
ligands (N Monodentates) to the high valence metal ion. N Valence
Stabilizer #19: Nitrosyl, nitrite, and related ligands where the
Nitrosyl and Nitrite and related ligands (N nitrogen atom is bound
directly to the high Monodentates) valence metal ion. N Valence
Stabilizer #20: R--CN, R--(CN).sub.2, R--(CN).sub.x, etc. where R
Nitriles, Dinitriles, and Polynitriles (N represents H or any
organic functional group Monodentates, N--N Bidentates, and N--N--N
wherein the number of carbon atoms ranges Tridentates) from 0 to
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. N Valence
Stabilizer #21: Azide (--N.sub.3) ligands bound directly to the
high Azide ligands (N Monodentates, or N--N valence metal ion. Also
includes organoazide Bidentates) derivatives (R--N.sub.3),
triazenido compounds (R-- N.sub.3--R'), phosphonyl azides
(R--PO.sub.2H--N.sub.3), phosphoryl azides (O--PO.sub.2H--N3), and
sulfonyl azides (R--SO.sub.2--N.sub.3) where R and R' represent H
or any organic functional group wherein the number of carbon atoms
ranges from 0 to 35, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached S Valence
Stabilizer #1: SH.sub.2, SHR, SR.sub.2, where R represents H or any
Monothioethers (S Monodentates) wherein organic functional group
wherein the number of at least one Sulfur Atom is a Binding Site
carbon atoms ranges from 0 to 35, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #2: R--S--S--R', where R and R' represents H or
any Disulfides (S Monodentates) wherein at organic functional group
wherein the number of least one Sulfur Atom is a Binding Site
carbon atoms ranges from 0 to 35, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #3: R--S--R'--S--R", where R, R', and R"
represents H Dithioethers (S--S Bidentates) wherein at or any
organic functional group wherein the least one Sulfur Atom is a
Binding Site number of carbon atoms ranges from 0 to 35, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, O, S, or
Se atoms. S Valence Stabilizer #4: R--S--R'--S--R"--S--R"', where
R, R', R", and R"' Trithioethers (S--S Bidentates or S--S
represents H or any organic functional group Tridentates) wherein
at least one Sulfur wherein the number of carbon atoms ranges Atom
is a Binding Site from 0 to 35, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #5: R--S--R'--S--R"--S--R"'--S--R"", where R,
R', R", Tetrathioethers (S--S Bidentates, S--S R"', and R""
represents H or any organic Tridentates, or S--S Bidentates)
wherein at functional group wherein the number of carbon least one
Sulfur Atom is a Binding Site atoms ranges from 0 to 35, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, O, S, or
Se atoms. S Valence Stabilizer #6:
R--S--R'--S--R"--S--R"'--S--R""--S--R""'--S--R"- "", Hexathioethers
(S--S Bidentates, S--S where R, R', R", R"', R"", R""', and R"""
Tridentates, S--S Tetradentates, or S--S represents H or any
organic functional group Hexadentates) wherein at least one Sulfur
wherein the number of carbon atoms ranges Atom is a Binding Site
from 0 to 35, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer
#7: Five membered heterocyclic ring containing one Five-Membered
Heterocyclic Rings or two sulfur atoms, both of which may function
containing One or Two Sulfur Atoms as binding sites. Can include
other ring systems wherein at least one Sulfur Atom is a bound to
this heterocyclic ring, but they do not Binding Site (S
Monodentates or S--S coordinate with the stabilized, high valence
Bidentates) metal ion. Ring can also contain O, N, P, As, or Se
atoms. This 5-membered ring and/or attached, uncoordinating rings
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#8: Six membered heterocyclic ring containing just Six-Membered
Heterocyclic Rings one or two sulfur atoms, both of which may
containing One or Two Sulfur Atoms function as binding sites. Can
include other wherein at least one Sulfur Atom is a ring systems
bound to this heterocyclic ring, but Binding Site (S Monodentates
or S--S they do not coordinate with the stabilized, high
Bidentates) valence metal ion. Ring can also contain O, N, P, As,
or Se atoms. This 5-membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#9: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at contains additional
sulfur-containing least one additional Sulfur Atom Binding
substituents (usually thiols or thioethers) that Site not in a Ring
(S Monodentates, S--S constitute S binding sites. Can include other
Bidentates, S--S Tridentates, S--S ring systems bound to the
heterocyclic ring or to Tetradentates, or S--S Hexadentates) the
S-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, N,
P, As or Se atoms. This 5-membered ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#10: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at contains additional
sulfur-containing least one additional Sulfur Atom Binding
substituents (usually thiols or thioethers) that Site not in a Ring
(S Monodentates, S--S constitute S binding sites. Can include other
Bidentates, S--S Tridentates, S--S ring systems bound to the
heterocyclic ring or to Tetradentates, or S--S Hexadentates) the
S-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, N,
P, As or Se atoms. This 6-membered ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#11: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at contains additional
sulfur-containing rings that least one additional Sulfur Atom
Binding constitute S binding sites. Can include other Site in a
separate Ring (S Monodentates, S-- ring systems bound to the
S-containing S Bidentates, S--S Tridentates, S--S heterocyclic
rings, but they do not coordinate Tetradentates, or S--S
Hexadentates) with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, P, As, or Se atoms. This 5-membered ring(s)
and/or additional S-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. S Valence
Stabilizer #12: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one or two sulfur atoms. In
addition, ligand containing One or Two Sulfur Atoms at contains
additional sulfur-containing rings that least one additional Sulfur
Atom Binding constitute S binding sites. Can include other Site in
a separate Ring (S Monodentates, S-- ring systems bound to the
S-containing S Bidentates, S--S Tridentates, S--S heterocyclic
rings, but they do not coordinate Tetradentates, or S--S
Hexadentates) with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, P, As, or Se atoms. This 6-membered ring(s)
and/or additional S-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. S Valence
Stabilizer #13: Macrocyclic ligands containing two to ten sulfur
Two-, Three-, Four-, Five-, Six-, Seven-, binding sites to valence
stabilize the central Eight-, Nine-, and Ten-Membered metal ion.
Can include other hydrocarbon or Macrocyclics, Macrobicyclics, and
ring systems bound to this macrocyclic ligand, Macropolycyclics
(including Catapinands, but they do not coordinate with the
stabilized, Cryptands, Cyclidenes, and Sepulchrates) high valence
metal ion. This ligand and/or wherein all Binding Sites are
composed of attached, uncoordinating hydrocarbons/rings Sulfur
(usually thiol or thioether groups) may or may not have halogen or
polarizing or and are not contained in Component
water-insolubilizing/solubilizing groups Heterocyclic Rings (S--S
Bidentates, S--S attached. Tridentates, S--S Tetradentates, and
S--S Hexadentates) S Valence Stabilizer #14: Macrocyclic ligands
containing a total of four to Four-, Five-, Six-, Seven-, Eight-,
Nine-, or ten five-membered heterocyclic rings containing
Ten-Membered Macrocyclics, sulfur binding sites. Can include other
Macrobicyclics, and Macropolycyclics hydrocarbon/ring systems bound
to this (including Catapinands, Cryptands, macrocyclic ligand, but
they do not coordinate Cyclidenes, and Sepulchrates) wherein all
with the stabilized, high valence metal ion. This Binding Sites are
composed of Sulfur and ligand and/or attached, uncoordinating are
contained in Component 5-Membered hydrocarbon/rings may or may not
have halogen Heterocyclic Rings (S--S Tridentates, S--S or
polarizing or water-insolubilizing groups Tetradentates or S--S
Hexadentates) attached. S Valence Stabilizer #15: Macrocyclic
ligands containing at least one 5- Four-, Five-, Six-, Seven-,
Eight-, Nine-, or membered heterocyclic ring. These Ten-Membered
Macrocyclics, heterocyclic rings provide sulfur binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, thiol,
thioether, or thioketo binding sites can Cyclidenes, and
Sepulchrates) wherein all also be included in the macrocyclic
ligand, so Binding Sites are composed of Sulfur and long as the
total number of binding sites is four are contained in a
Combination of 5- to ten. Can include other hydrocarbon/ring
Membered Heterocyclic Rings and Thiol, systems bound to this
macrocyclic ligand, but Thioether, or Thioketo Groups (S--S they do
not coordinate with the stabilized, high Tridentates, S--S
Tetradentates, or S--S valence metal ion. This ligand and/or
attached, Hexadentates) uncoordinating hydrocarbon/rings may or may
not have halogen or polarizing or water- insolubilizing groups
attached. S Valence Stabilizer #16: Macrocyclic ligands containing
a total of four to Four-, Five-, Six-, Seven-, Eight-, Nine-, or
ten six-membered heterocyclic rings containing Ten-Membered
Macrocyclics, sulfur binding sites. Can include other
Macrobicyclics, and Macropolycyclics hydrocarbon/ring systems bound
to this (including Catapinands, Cryptands, macrocyclic ligand, but
they do not coordinate Cyclidenes, and Sepulchrates) wherein all
with the stabilized, high valence metal ion. This Binding Sites are
composed of Sulfur and ligand and/or attached, uncoordinating are
contained in Component 6-Membered hydrocarbon/rings may or may not
have halogen Heterocyclic Rings (S--S Tridentates, S--S or
polarizing or water-insolubilizing groups Tetradentates, or S--S
Hexadentates) attached. S Valence Stabilizer #17: Macrocyclic
ligands containing at least one 6- Four-, Five-, Six-, Seven-,
Eight-, Nine-, or membered heterocyclic ring. These Ten-Membered
Macrocyclics, heterocyclic rings provide sulfur binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, thiol,
thioether, or thioketo binding sites can Cyclidenes, and
Sepulchrates) wherein all also be included in the macrocyclic
ligand, so Binding Sites are composed of Sulfur and long as the
total number of binding sites is four are contained in a
Combination of 6- to ten. Can include other hydrocarbon/ring
Membered Heterocyclic Rings and Thiol, systems bound to this
macrocyclic ligand, but Thioether, or Thioketo Groups (S--S they do
not coordinate with the stabilized, high Tridentates, S--S
Tetradentates, or S--S valence metal ion. This ligand and/or
attached, Hexadentates) uncoordinating hydrocarbon/rings may or may
not have halogen or polarizing or water- insolubilizing groups
attached. S Valence Stabilizer #18:
RR'--N--C(.dbd.S)--NR"--C(.dbd.S)--NR"'R"" for Dithiobiurets
(Dithioimidodicarbonic dithiobiurets, and
RR'--N--C(.dbd.S)--NR"--NH-- Diamides), Dithioisobiurets,
Dithiobiureas, C(.dbd.S)--NR"'R"" for dithiobiureas, where R, R',
Trithiotriurets, Trithiotriureas, R", R"', and R"" represent H,
NH.sub.2, or any Bis(dithiobiurets), Bis(dithioisobiurets), organic
functional group wherein the number of Bis(dithiobiureas),
Poly(dithiobiurets), carbon atoms ranges from 0 to 40, optionally
Poly(dithioisobiurets), and having halogen or polarizing or water-
Poly(dithiobiureas) (S--S Bidentates, S--S
insolubilizing/solubilizing groups attached. Tridentates, S--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #19: RR'--N--C(.dbd.S)--NR"--C(.dbd.S)-
--R"' where R, R', R", Thioacylthioureas, Thioaroylthioureas, and
R"' represent H, NH.sub.2, or any organic Bis(thioacylthioureas),
functional group wherein the number of carbon
Bis(thioaroylthioureas), atoms ranges from 0 to 40, optionally
having Poly(thioacylthioureas), and halogen or polarizing or water-
Poly(thioaroylthioureas) (S--S Bidentates, S--
insolubilizing/solubilizin- g groups attached. S Tridentates, S--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #20:
R--C(.dbd.S)--S--S--C--(.dbd.S)--R' where R, and R' Dithioacyl
disulfides, Bis(dithioacyl represent H or any organic functional
group disulfides), and Poly(dithioacyl disulfides) wherein the
number of carbon atoms ranges (S--S Bidentates, S--S Tridentates,
S--S from 0 to 40, optionally having halogen or Tetradentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #21: RR'--N--C(.dbd.S)--S--S--C(.dbd.S- )--N--R"R"'
where R, R', Tetrathioperoxydicarbonic Diamides, R", R"' represent
H or any organic functional Bis(tetrathioperoxydicar- bonic
diamides), group wherein the number of carbon atoms and
poly(tetrathioperoxydicarbonic ranges from 0 to 40, optionally
having halogen diamides) (S--S Bidentates, S--S Tridentates, or
polarizing or water- S--S Tetradentates) insolubilizing/solubilizi-
ng groups attached. Ligand can also contain nonbinding N, O, S, or
P atoms. S Valence Stabilizer #22: R--S--C(.dbd.S)--S--S---
C(.dbd.S)--S--R' for Hexathio-, Pentathio-, and
hexathioperoxydicarbonic acids, R--O--C(.dbd.S)--S--
Tetrathioperoxydicarbonic Acids, S--C(.dbd.S)--S--R' for
pentathioperoxydicarbonic Bis(hexathio-, pentathio-, and acids, and
R--O--C(.dbd.S)--S--S--C(.dbd.S)--O--R' for
tetrathioperoxydicarbonic acids), tetrathioperoxydicarbonic acids,
where R and R' poly(hexathio-, pentathio-, and represent H,
NH.sub.2 or any organic functional tetrathioperoxydicarbonic
acids), and group wherein the number of carbon atoms derivatives
thereof (S--S Bidentates, S--S ranges from 0 to 40, optionally
having halogen Tridentates, S--S Tetradentates) or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #23:
(RR'--N--)(RR"R"'--N--)P(.dbd.S)--S--S--P(.dbd.S)(--N--
Dithioperoxydiphosphoramide, R""R""')(--N--R"""R"""'), where R, R',
R", R"', Bis(dithioperoxyphosphoramide), and R"", R""', R""", and
R"""' represent H, NH.sub.2 or Poly(dithioperoxydiphosphoramide)
(S--S any organic functional group wherein the Bidentates, S--S
Tridentates, S--S number of carbon atoms ranges from 0 to 40,
Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #24:
(R--O--)(R'--O--)P(.dbd.S)--S--S--P(.dbd.S)(--O--R")(--O-- -
Dithioperoxydiphosphoric Acids, R"'); (R--O--)(R'--S--)P(.dbd.S)--
-S--S--P(.dbd.S)(--S--R")(--O-- Bis(dithioperoxyphosphoric Acids),
R"'); or (R--S--)(R'--S--)P(.dbd.S)--S--S--P(.dbd.S)(--S--R")(--
Poly(dithioperoxydiphosphoric Acids), and S--R"'), where R, R', R",
R"', R"", R""', R""", derivatives thereof (S--S Bidentates, S--S
and R"""' represent H, NH.sub.2 or any organic Tridentates, S--S
Tetradentates) functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #25:
(R--O--)(R'--)P(.dbd.S)--NH--P(.dbd.S)(--R- ")(--O--R"'); (R--
Dithioimidodiphosphonic Acids,
S--)(R'--)P(.dbd.S)--NH--P(.dbd.S)(--R")(--O--R"'); or (R--
Dithiohydrazidodiphosphonic Acids,
S--)(R'--)P(.dbd.S)--NH--P(.dbd.S)(--R- ")(--S--R"') for
Bis(dithioimidodiphosphonic acids), dithioimidodiphosphonic acids,
and --NH--NH-- Bis(dithiohydrazidodiphosphonic acids), derivatives
for dithiohydrazidodiphosphonic Poly(dithioimidodiphosphonic
acids), acids, where R, R', R", and R"' represent H,
Poly(dithiohydrazidodiphosphonic acids), NH.sub.2 or any organic
functional group wherein and derivatives thereof (S--S Bidentates,
S--S the number of carbon atoms ranges from 0 to Tridentates, and
S--S Tetradentates) 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #26:
(RR'--N--)(R"--)P(.dbd.S)--NH--P(.dbd.S)(--R"')(--N--
Dithioimidodiphosphonamides, R""R""') for
dithioimidophosphonamides, and Dithiohydrazidodiphosphonamides,
(RR'--N--)(R"--)P(.dbd.S)--NH- --NH--P(.dbd.S)(--R"')(--N--
Bis(dithioimidodiphosphonamides), R""R""') for
Bis(dithiohydrazidodiphosphonamides),
dithiohydrazidodiphosphonamides, where R, R',
Poly(dithioimidodiphosphonamides), and R", R"', R"", and R""'
represent H, NH.sub.2 or any Poly(dithiohydrazidodiphosphonamides)
organic functional group wherein the number of (S--S Bidentates,
S--S Tridentates, S--S carbon atoms ranges from 0 to 40, optionally
Tetradentates) having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #27:
(RR'--N--)(R"--)P(.dbd.S)--S--P(.dbd.S)(--R"')(--N--
Dithiodiphosphonamides, R""R""'), or
(RR'--N--)(R"--)p(.dbd.S)--O--P--(- .dbd.S)(--
Bis(dithiophosphonamides), and R"')(--N--R""R""'), where R, R', R",
R"', R"", Poly(dithiodiphosphonamides) (S--S and R""' represent H,
NH.sub.2 or any organic Bidentates, S--S Tridentates, S--S
functional group wherein the number of carbon Tetradentates) atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #28:
(R--O--)(R'--)P(.dbd.S)--O--P(.dbd.S)(--R"- )(--O--R"'); (R--O--)
Dithiodiphosphonic Acids,
(R'--)P(.dbd.S)--S--P(.dbd.S)(--R")(--O--R"'); (R--S--)(R'--)
Bis(dithioiphosphonic Acids),
P(.dbd.S)--O--P(.dbd.S)(--R")(--S--R"'); or (R--S--)(R'--)
Poly(dithiodiphosphonic Acids), and
P(.dbd.S)--S--P(.dbd.S)(--R")(--S--R"'); where R, R', R",
derivatives thereof (S--S Bidentates, S--S and R"' represent H,
NH.sub.2 or any organic Tridentates, S--S Tetradentates) functional
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #29:
(RR'--N--)(R"--)P(.dbd.S)--S--S--P(.dbd.S)(--R"')(--N--
Dithioperoxydiphosphonamide, R""R""'), where R, R', R", R"', R"",
and R""' Bis(dithioperoxyphosphonamide), and represent H, NH.sub.2
or any organic functional Poly(dithioperoxydiphosphonamide) (S--S
group wherein the number of carbon atoms Bidentates, S--S
Tridentates, S--S ranges from 0 to 40, optionally having halogen
Tetradentates) or polarizing or water- insolubilizing/solubilizin-
g groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #30: (R--O--)(R'--)P(.dbd.S)-
--S--S--P(.dbd.S)(--R")(--O--R"'); or Dithioperoxydiphosphonic
Acids, (R--S--)(R'--)P(.dbd.S)--S--S--P(.dbd.S)(--R")(--S--R"'),
Bis(dithioperoxyphosphonic Acids), where R, R', R", and R"'
represent H, NH.sub.2 or Poly(dithioperoxydiphosphonic Acids), and
any organic functional group wherein the derivatives thereof (S--S
Bidentates, S--S number of carbon atoms ranges from 0 to 40,
Tridentates, S--S Tetradentates) optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #31: Dithiophosphonic (O.dbd.)PR(--S--R')(--S--R") or
(S.dbd.)PR(--S--R')(--O-- Acids (Phosphonodithioic Acids), R"),
where R, R', and R" represent H, NH.sub.2 or Bis(dithiophosphonic
Acids), any organic functional group wherein the
Poly(dithiophosphonic Acids), and number of carbon atoms ranges
from 0 to 40, derivatives thereof (S--S Bidentates, S--S optionally
having halogen or polarizing or Tridentates, S--S Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #32:
(S.dbd.)PR(--S--R')(--S--R"), where R, R', and R" Trithiophosphonic
Acids represent H, NH.sub.2 or any organic functional
(Phosphonotrithioic Acids), group wherein the number of carbon
atoms Bis(trithiophosphonic Acids), ranges from 0 to 40, optionally
having halogen Poly(trithiophosphonic Acids), and or polarizing or
water- derivatives thereof (S--S Bidentates, S--S
insolubilizing/solubilizing groups attached. Tridentates, S--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #33: (O.dbd.)PR(--S--S--R')(--S--R") or
(S.dbd.)PR(--S--S--R')(-- Phosphono(dithioperoxo)thioic Acids),
O--R"), where R, R', and R" represent H, NH.sub.2 or
Bis[phosphono(dithioperoxo)thioic Acids], any organic functional
group wherein the Poly[phosphono(dithioperoxo)thioic number of
carbon atoms ranges from 0 to 40, Acids], and derivatives thereof
(S--S optionally having halogen or polarizing or Bidentates, S--S
Tridentates, S--S water-insolubilizing/solubilizing groups
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. S Valence Stabilizer #34: (S.dbd.)PR(--S--S--R')(---
S--R"), where R, R', and R" Phosphono(dithioperoxo)dithioic Acids),
represent H, NH.sub.2 or any organic functional
Bis[phosphono(dithioperoxo)dithioic group wherein the number of
carbon atoms Acids], ranges from 0 to 40, optionally having halogen
Poly[phosphono(dithioperoxo)dithioic or polarizing or water-
Acids], and derivatives thereof (S--S insolubilizing/solubilizing
groups attached. Bidentates, S--S Tridentates, S--S Ligand can also
contain nonbinding N, O, S, or Tetradentates) P atoms. S Valence
Stabilizer #35: R--S--R'CSOH or R--S--R'CSSH for S--
S--(Alkylthio)thiocarboxylic Acids, S-- (alkylthio)thiocarboxylic
and S-- (Arylthio)thiocarboxylic Acids, and S,S--
(arylthio)thiocarboxylic acids, and HSOCR--S--
thiobisthiocarboxylic Acids (S--S Bidentates R'COSH or
HSSCR--S--R'CSSH for S,S-- and S--S Tridentates)
thiobisthiocarboxylic acids, where R and R' represent H or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #36:
R--S--S--R'CSOH or R--S--S--R'CSSH for S--
S--(Alkyldisulfido)thiocarboxylic Acids, S--
(alkyldisulfido)thiocarboxyl- ic and S--
(Aryldisulfido)thiocarboxylic Acids, and
(aryldisulfido)thiocarboxylic acids, and S,S'--Disulfidobisthiocar-
boxylic Acids (S--S HSOCR--S--S--R'COSH or HSSCR--S--S--R'CSSH
Bidentates and S--S Tridentates) for
S,S'--disulfidobisthiocarboxylic acids, where R and R' represent H
or any organic functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #37:
R--CH(--SR")--CH(--SR"')--R', and R--C(-- 1,2-Dithiolates,
Bis(1,2-dithiolates), and SR").dbd.C(--SR"')--R', where R, R', R",
and R"' Poly(1,2-dithiolates) (S--S Bidentates, S--S represent H,
NH.sub.2 or any organic functional Tridentates, S--S Tetradentates)
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #38:
RN--C(.dbd.O)--CHR'--S--C(.dbd.S) for rhodanines, and Rhodanines
and Bis(rhodanines) (S--S R--[N--C(.dbd.O)--CHR'--S--C(.dbd-
.S)].sub.2 for Bidentates and S--S Tetradentates) bis(rhodanines),
where R and R' represent H, NH.sub.2 or any organic functional
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #39:
RN.dbd.C(SH)(SH), where R represents H, NH.sub.2 or
Dithiocarbimates, Bis(dithiocarbimates), any organic functional
group wherein the and Poly(dithiocarbimates) (S--S Bidentates,
number of carbon atoms ranges from 0 to 40, S--S Tridentates, and
S--S Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #40:
RS.sup.+.dbd.C(SH)(SH) or RS--C(.dbd.S)(SH), where R Thioxanthates,
Bis(thioxanthates), and represents H, NH.sub.2 or any organic
functional Poly(thioxanthates) (S--S Bidentates and S--S group
wherein the number of carbon atoms Tetradentates) ranges from 0 to
40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #41:
RO.sup.+.dbd.C(SH)(SH) or RO--C(.dbd.S)(SH), where R Xanthates,
Bis(xanthates), and represents H, NH.sub.2 or any organic
functional Poly(xanthates) (S--S Bidentates and S--S group wherein
the number of carbon atoms Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #42:
Typically RR'R"P.dbd.C(SH)(SH) [pentavalent P],
Phosphinodithioformates (S--S Bidentates) although
RR'P--C(.dbd.S)(SH) [trivalent P] may be acceptable in some
situations, where R, R', and R" represent H, NH.sub.2 or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #43:
R--S--C(--S--R")--O--R' for dithioborates, R--S--C(--S-- Alkyl- and
Aryl- Dithioborates, R")--S--R' for trithioborates, and
R--S--S--C(--S-- Trithioborates, Perthioborates, R")--S--R' for
perthioborates, where R, R', and Bis(dithioborates),
Bis(trithioborates), and R" represent H, NH.sub.2 or any organic
functional Bis(perthioborates) (S--S Bidentates and S--S group
wherein the number of carbon atoms Tetradentates) ranges from 0 to
40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #44:
R--C(--S--R")--S--R', where R, R', and R" Alkyl- and Aryl-
Dithioboronates, and represent H, NH.sub.2 or any organic
functional Bis(dithioboronates) (S--S Bidentates and S--S group
wherein the number of carbon atoms Tetradentates) ranges from 0 to
40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #45:
(O.dbd.)As(--S--R)(--S--R')(--S--R") or (S.dbd.)As(--S--R)(--
Trithioarsonic Acids (Arsonotrithioic S--R')(--O--R") for
trithioarsonic acid; (O.dbd.)As(-- Acids), Dithioarsonic Acids
O--R)(--S--R')(--S--R") or (S.dbd.)As(--S--R)(--O--R'- )(--
(Arsonodithioic Acids), Tetrathioarsonic O--R") for dithioarsonic
acid, or (S.dbd.)As(--S--R)(-- Acids (Arsonotetrathioic Acids), and
S--R')(--S--R") for tetrathioarsonic acid, where R, derivatives
thereof (S--S Bidentates, S--S R', and R" represent H, NH.sub.2 or
any organic Tridentates, S--S Tetradentates) functional group
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #46:
(O.dbd.)Sb(--S--R)(--S--R')(--S--R") or (S.dbd.)Sb(--S--R)(--
Trithioantimonic Acids (Stibonotrithioic S--R')(--O--R") for
trithioantimonic acid; Acids), Dithioantimonic Acids
(O.dbd.)Sb(--O--R)(--S--R')(--S--R") or (S.dbd.)Sb(--S--R)(--
(Stibonodithioic Acids), Tetrathioantimonic O--R')(--O--R") for
dithioantimonic acid, or Acids (Stibonotetrathioic Acids), and
(S.dbd.)Sb(--S--R)(--S--R')(--S--R") for derivatives thereof (S--S
Bidentates, S--S tetrathioantimonic acid, where R, R', and R"
Tridentates, S--S Tetradentates) represent H, NH.sub.2 or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #47:
RR'R"P.dbd.S for phosphine P--sulfides, and Phosphine P--sulfides
and Amino- (RR'N)(R"R"'N)(R""R""'N)P.dbd.S for amino-- substituted
Phosphine sulfides (S substituted phosphine sulfides, where R, R',
R", Monodentates) R"', R"", and R""' represent H, Cl, Br, NH.sub.2
or any organic functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. (Rs are
typically aromatic or heterocyclic for phosphine P-sulfides.)
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #48: RR'R"As.dbd.S for arsine As-sulfides, and Arsine
As-sulfides and Amino-substituted (RR'N)(R"R"'N)(R""R""'N)A-
s.dbd.S for amino- Arsine sulfides (S Monodentates) substituted
arsine sulfides, where R, R', R", R"', R"", and R""' represent H,
Cl, Br, NH.sub.2 or any organic functional group wherein the number
of carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
(Rs are typically aromatic or heterocyclic for arsine As-sulfides.)
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #49: Thiols (HS--R, HS--R--SH, etc.), where R and R'
Thiolates (S Monodentates) represent H or any organic functional
group wherein the number of carbon atoms ranges from 0 to 35,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. S Valence
Stabilizer #50: Sulfide (--S.sup.2-) ligands bound directly to the
high Sulfide ligands (S Monodentates) valence metal ion. P Valence
Stabilizer #1: PH.sub.3, PH.sub.2R, PHR.sub.2, and PR.sub.3 where R
represents Monophosphines (P Monodentates) H or any organic
functional group wherein the wherein at least one Phosphorus Atom
is a number of carbon atoms ranges from 0 to 35, Binding Site
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #2: R'--P--R--P--R", where R, R', and R" represent H
Diphosphines (a P--P Bidentate) wherein at or any organic
functional group wherein the least one Phosphorus Atom is a Binding
number of carbon atoms ranges from 0 to 35, Site optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, P, As, O, S, or Se
atoms. P Valence Stabilizer #3: R--P--R'--P--R"--P--R"', where R,
R', R", and R"' Triphosphines (either P--P Bidentates or P-
represent H or any organic functional group P--P Tridentates)
wherein at least one wherein the number of carbon atoms ranges
Phosphorus Atom is a Binding Site from 0 to 35, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, P, As, O, S, or Se
atoms. P Valence Stabilizer #4: R--P--R'--P--R"--P--R"'--P--R"",
where R, R', R", Tetraphosphines (P--P Bidentates, P--P R"', and
R"" represent H or any organic Tridentates, or P--P Tetradentates)
wherein functional group wherein the number of carbon at least one
Phosphorus Atom is a Binding atoms ranges from 0 to 35, optionally
having Site halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #5: R--P--R'--P--R"--P--R"'--P--R""--P--R""', where R,
R', Pentaphosphines (P--P Bidentates, P--P R", R"', R"", and R""'
represent H or any Tridentates, or P--P Tetradentates) wherein
organic functional group wherein the number of at least one
Phosphorus Atom is a Binding carbon atoms ranges from 0 to 35,
optionally Site having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #6: R--P--R'--P--R"--P--R"'--P--R""--P--R""'--P--R""",
Hexaphosphines (P--P Bidentates, P--P where R, R', R", R"', R"",
R""', and R""" Tridentates, P--P Tetradentates, or P--P represent H
or any organic functional group Hexadentates) wherein at least one
wherein the number of carbon atoms ranges Phosphorus Atom is a
Binding Site from 0 to 35, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #7: Five membered heterocyclic ring containing
Five-Membered Heterocyclic Rings one, two, or three phosphorus
atoms, all of containing One, Two, or Three Phosphorus which may or
may not function as binding sites. Atoms wherein at least one
Phosphorus Can include other ring systems bound to this Atom is a
Binding Site (P Monodentates or heterocyclic ring, but they do not
coordinate P--P Bidentates) with the stabilized, high valence metal
ion. Ring can also contain O, S, N, As, or Se atoms. This
5-membered ring and/or attached, uncoordinating rings may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P Valence Stabilizer
#8: Six membered heterocyclic ring containing one, Six-Membered
Heterocyclic Rings two, or three phosphorus atoms, all of which
containing One, Two, or Three Phosphorus may or may not function as
binding sites. Can Atoms wherein at least one Phosphorus
include
other ring systems bound to this Atom is a Binding Site (P
Monodentates or heterocyclic ring, but they do not coordinate P--P
Bidentates) with the stabilized, high valence metal ion. Ring can
also contain O, S, N, As, or Se atoms. This 6-membered ring and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached. P
Valence Stabilizer #9: Five membered heterocyclic ring(s)
containing Five-Membered Heterocyclic Rings one, two, or three
phosphorus atoms. In containing One, Two, or Three Phosphorus
addition, ligand contains additional phosphorus- Atoms at least one
additional Phosphorus containing substituents (usually phosphines)
Atom Binding Site not in a Ring (P that constitute P binding sites.
Can include Monodentates, P--P Bidentates, P--P other ring systems
bound to the heterocyclic Tridentates, P--P Tetradentates, or P--P
ring or to the P-containing substituent, but they Hexadentates) do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, S, As or Se atoms. This 5-membered ring(s)
and/or attached, uncoordinating rings and/or P- containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P Valence Stabilizer
#10: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one, two, or three phosphorus atoms. In
containing One, Two, or Three Phosphorus addition, ligand contains
additional phosphorus- Atoms at least one additional Phosphorus
containing substituents (usually phosphines) Atom Binding Site not
in a Ring (P that constitute P binding sites. Can include
Monodentates, P--P Bidentates, P--P other ring systems bound to the
heterocyclic Tridentates, P--P Tetradentates, or P--P ring or to
the P-containing substituent, but they Hexadentates) do not
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, N, S, As or Se atoms. This 6-membered ring(s)
and/or attached, uncoordinating rings and/or P- containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P Valence Stabilizer
#11: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one, two, or three phosphorus atoms. In
containing One, Two, or Three Phosphorus addition, ligand contains
additional phosphorus- Atoms at least one additional Phosphorus
containing rings that constitute P binding sites. Atom Binding Site
in a separate Ring (P Can include other ring systems bound to the
P- Monodentates, P--P Bidentates, P--P containing heterocyclic
rings, but they do not Tridentates, P--P Tetradentates, or P--P
coordinate with the stabilized, high valence Hexadentates) metal
ion. Ring(s) can also contain O, N, S, As, or Se atoms. This
5-membered ring(s) and/or additional P-containing ring(s) and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached. P
Valence Stabilizer #12: Six membered heterocyclic ring(s)
containing Six-Membered Heterocyclic Rings one, two, or three
phosphorus atoms. In containing One, Two, or Three Phosphorus
addition, ligand contains additional phosphorus- Atoms at least one
additional Phosphorus containing rings that constitute P binding
sites. Atom Binding Site in a separate Ring (P Can include other
ring systems bound to the P- Monodentates, P--P Bidentates, P--P
containing heterocyclic rings, but they do not Tridentates, P--P
Tetradentates, or P--P coordinate with the stabilized, high valence
Hexadentates) metal ion. Ring(s) can also contain O, N, S, As, or
Se atoms. This 6-membered ring(s) and/or additional P-containing
ring(s) and/or attached, uncoordinating rings may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. P Valence Stabilizer #13: Macrocyclic ligands containing
two, three, four, two-, Three-, Four-, Five-, Six-, and Eight-
five, six, or eight phosphorus binding sites to Membered
Macrocyclics, Macrobicyclics, valence stabilize the central metal
ion. Can and Macropolycyclics (including include other hydrocarbon
or ring systems Catapinands, Cryptands, Cyclidenes, and bound to
this macrocyclic ligand, but they do Sepulchrates) wherein all
Binding Sites are not coordinate with the stabilized, high valence
composed of Phosphorus and are not metal ion. This ligand and/or
attached, contained in Component Heterocyclic uncoordinating
hydrocarbons/rings may or may Rings (P--P Bidentates, P--P
Tridentates, P--P not have halogen or polarizing or water-
Tetradentates, and P--P Hexadentates) insolubilizing/solubilizing
groups attached. P Valence Stabilizer #14: Macrocyclic ligands
containing a total of four, Four-, six-, or Eight-Membered six, or
eight five-membered heterocyclic rings Macrocyclics,
Macrobicyclics, and containing phosphorus binding sites. Can
Macropolycyclics (including Catapinands, include other
hydrocarbon/ring systems bound Cryptands, Cyclidenes, and
Sepulchrates) to this macrocyclic ligand, but they do not wherein
all Binding Sites are composed of coordinate with the stabilized,
high valence Phosphorus and are contained in metal ion. This ligand
and/or attached, Component 5-Membered Heterocyclic uncoordinating
hydrocarbon/rings may or may Rings (P--P Tridentates, P--P
Tetradentates, not have halogen or polarizing or water- or P--P
Hexadentates) insolubilizing groups attached. P Valence Stabilizer
#15: Macrocyclic ligands containing at least one 5- Four-, six-, or
Eight-Membered membered heterocyclic ring. These Macrocyclics,
Macrobicyclics, and heterocyclic rings provide phosphorus binding
Macropolycyclics (including Catapinands, sites to valence stabilize
the central metal ion. Cryptands, Cyclidenes, and Sepulchrates)
Other phosphine binding sites can also be wherein all Binding Sites
are composed of included in the macrocyclic ligand, so long as
Phosphorus and are contained in a the total number of binding sites
is four, six, or Combination of 5-Membered Heterocyclic eight. Can
include other hydrocarbon/ring Rings and Phosphine Groups (P--P
systems bound to this macrocyclic ligand, but Tridentates, P--P
Tetradentates, or P--P they do not coordinate with the stabilized,
high Hexadentates) valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. P Valence
Stabilizer #16: Macrocyclic ligands containing a total of four,
Four-, six-, or Eight-Membered six, or eight six-membered
heterocyclic rings Macrocyclics, Macrobicyclics, and containing
phosphorus binding sites. Can Macropolycyclics (including
Catapinands, include other hydrocarbon/ring systems bound
Cryptands, Cyclidenes, and Sepulchrates) to this macrocyclic
ligand, but they do not wherein all Binding Sites are composed of
coordinate with the stabilized, high valence Phosphorus and are
contained in metal ion. This ligand and/or attached, Component
6-Membered Heterocyclic uncoordinating hydrocarbon/rings may or may
Rings (P--P Tridentates, P--P Tetradentates, not have halogen or
polarizing or water- or P--P Hexadentates) insolubilizing groups
attached. P Valence Stabilizer #17: Macrocyclic ligands containing
at least one 6- Four-, six-, or Eight-Membered membered
heterocyclic ring. These Macrocyclics, Macrobicyclics, and
heterocyclic rings provide phosphorus binding Macropolycyclics
(including Catapinands, sites to valence stabilize the central
metal ion. Cryptands, Cyclidenes, and Sepulchrates) Other phosphine
binding sites can also be wherein all Binding Sites are composed of
included in the macrocyclic ligand, so long as Phosphorus and are
contained in a the total number of binding sites is four, six, or
Combination of 6-Membered Heterocyclic eight. Can include other
hydrocarbon/ring Rings and Phosphine Groups (P--P systems bound to
this macrocyclic ligand, but Tridentates, P--P Tetradentates, or
P--P they do not coordinate with the stabilized, high Hexadentates)
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. O Valence Stabilizer #1:
R--O--C(.dbd.O)--S--S--C(.dbd.O- )--O--R', where R and R'
Dithioperoxydicarbonic Acids, represent H, NH.sub.2 or any organic
functional Bis(dithioperoxydicarbonic acids), group wherein the
number of carbon atoms poly(dithioperoxydicarbonic acids), and
ranges from 0 to 40, optionally having halogen derivatives thereof
(O--O Bidentates, O--O or polarizing or water- Tridentates, O--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #2:
(R--O--)(R'--)P(.dbd.O)--NH--P(.dbd.O)(--R")(--O--R"') for
Imidodiphosphonic Acids, imidodiphosphonic acids, and
(R--O--)(R'--) Hydrazidodiphosphonic Acids,
P(.dbd.O)--NH--NH--P(.dbd.O)(--R")(--O--R"') for
Bis(imidodiphosphonic Acids), hydrazidodiphosphonic acids; where R,
R', R", Bis(hydrazidodiphosphonic Acids), and R"' represent H,
NH.sub.2 or any organic Poly(imidodiphosphonic Acids), functional
group wherein the number of carbon Poly(hydrazidodiphosphonic
Acids), and atoms ranges from 0 to 40, optionally having
derivatives thereof (O--O Bidentates, O--O halogen or polarizing or
water- Tridentates, O--O Tetradentates) insolubilizing/solubilizin-
g groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #3: (RR'--N--)(R"--)P(.dbd.O-
)--NH--P(.dbd.O)(--R"')(--N-- Imidodiphosphonamides, R""R""') for
imidodiphosphonamides, and -- Hydrazidodiphosphonamides,
NH--NH--derivatives for Bis(imidodiphosphonamides),
hydrazidodiphosphonamides, where R, R', R",
Bis(hydrazidodiphosphonamides), R"', R"", and R""' represent H,
NH.sub.2 or any Poly(imidodiphosphonamides), and organic functional
group wherein the number of Poly(hydrazidodiphosphonamides) (O--O
carbon atoms ranges from 0 to 40, optionally Bidentates, O--O
Tridentates, O--O having halogen or polarizing or water-
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #4: (RR'--N--)(R"--)P(.dbd.O)--O--P(.dbd.O)(--R"')(--N-
-- Diphosphonamides, R""R""'), where R, R', R", R"', R"", and R""'
Bis(diphosphonamides), and represent H, NH.sub.2 or any organic
functional Poly(diphosphonamides) (O--O Bidentates, group wherein
the number of carbon atoms O--O Tridentates, O--O Tetradentates)
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #5:
R--O--C(.dbd.O)--O--R', where R, and R' represent H, Carbonates and
Bis(carbonates) (O--O NH.sub.2 or any organic functional group
wherein Bidentates and O--O Tetradentates) the number of carbon
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer
#6: RR'N--NR"--C(.dbd.O)(OH), where R and R' Carbazates
(carbazides), Bis(carbazates), represent H, NH.sub.2 or any organic
functional and Poly(carbazates) (O--O Bidentates, O--O group
wherein the number of carbon atoms Tridentates, and O--O
Tetradentates; or ranges from 0 to 40, optionally having halogen
possibly N--O Bidentates, N--O Tridentates, or polarizing or water-
and N--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #7: (O.dbd.)As(--O--R)(--O--R')(--O--R"), where
R, R', and Arsonic Acids, Bis(arsonic acids), R" represent H,
NH.sub.2 or any organic functional Poly(arsonic acids), and
derivatives thereof group wherein the number of carbon atoms (O--O
Bidentates, O--O Tridentates, O--O ranges from 0 to 40, optionally
having halogen Tetradentates) or polarizing or water-
insolubilizing/solubilizin- g groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #8:
R--O--C(--O--R")--O--R', where R, R', and R" Alkyl- and Aryl-
Borates and Bis(borates) represent H, NH.sub.2 or any organic
functional (O--O Bidentates and O--O Tetradentates) group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #9: R--C(--O--R")--O--R', where R, R', and R"
Alkyl- and Aryl- Boronates and represent H, NH.sub.2 or any organic
functional Bis(boronates) (O--O Bidentates and O--O group wherein
the number of carbon atoms Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #10:
RR'R"P.dbd.O for phosphine P-oxides, and Phosphine P-oxides and
Amino-substituted (RR'N)(R"R"'N)(R""R""'N)P.dbd.O for amino-
Phosphine oxides (O Monodentates) substituted phosphine oxides,
where R, R', R", R"',R"", and R""', represent H, Cl, Br, NH.sub.2
or any organic functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. (Rs are
typically aromatic or heterocyclic for phosphine P-oxides.) Ligand
can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #11: RR'R"As.dbd.O for arsine As-oxides, and Arsine
As-oxides and Amino-substituted (RR'N)(R"R"'N)(R""R""'N)As.dbd.O
for amino- Arsine oxides (O Monodentates) substituted arsine
oxides, where R, R', R", R"', R"", and R""' represent H, Cl, Br,
NH.sub.2 or any organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
(Rs are typically aromatic or heterocyclic for arsine As-oxides.)
Ligand can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #12: Five membered heterocyclic ring containing one
Five-Membered Heterocyclic Rings or two oxygen atoms, both of which
may or containing One or Two Oxygen Atoms may not function as
binding sites. Can include wherein at least one Oxygen Atom is a
other ring systems bound to this heterocyclic Binding Site (O
Monodentates or O--O ring, but they do not coordinate with the
Bidentates) stabilized, high valence metal ion. Ring can also
contain O, S, or P atoms. This 5-membered ring and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. O Valence
Stabilizer #13: Six membered heterocyclic ring containing one
Six-Membered Heterocyclic Rings or two oxygen atoms, both of which
may or containing One or Two Oxygen Atoms may not function as
binding sites. Can include wherein at least one Oxygen Atom is a
other ring systems bound to this heterocyclic Binding Site (O
Monodentates or O--O ring, but they do not coordinate with the
Bidentates) stabilized, high valence metal ion. Ring can also
contain O, S, or P atoms. This 6-membered ring and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. O Valence
Stabilizer #14: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one or two oxygen atoms. In
addition, ligand containing One or Two Oxygen Atoms and contains
additional oxygen-containing having at least one additional Oxygen
Atom substituents (usually hydroxyl or ester groups) Binding Site
not in a Ring (O that constitute O binding sites. Can include
Monodentates, O--O Bidentates, O other ring systems bound to the
heterocyclic Tridentates, O Tetradentates, or O ring or to the
O-containing substituent, but they Hexadentates) do not coordinate
with the stabilized, high valence metal ion. Ring(s) can also
contain O, S, or P atoms. This 5-membered ring(s) and/or attached,
uncoordinating rings and/or O- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. O Valence Stabilizer
#15: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and contains additional
oxygen-containing having at least one additional Oxygen Atom
substituents (usually hydroxyl or ester groups) Binding Site not in
a Ring (O that constitute O binding sites. Can include
Monodentates, O--O Bidentates, O other ring systems bound to the
heterocyclic Tridentates, O Tetradentates, or O ring or to the
O-containing substituent, but they Hexadentates) do not coordinate
with the stabilized, high valence metal ion. Ring(s) can also
contain O, S, or P atoms. This 6-membered ring(s) and/or attached,
uncoordinating rings and/or O- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. O Valence Stabilizer
#16: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and contains additional
oxygen-containing rings that having at least one additional Oxygen
Atom constitute O binding sites. Can include other Binding Site in
a Separate Ring (O ring systems bound to the O-containing
Monodentates, O--O Bidentates, O heterocyclic rings, but they do
not coordinate Tridentates, O Tetradentates, or O with the
stabilized, high valence metal ion. Hexadentates) Ring(s) can also
contain O, S, or P atoms. This 5-membered ring(s) and/or additional
O- containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. O Valence Stabilizer
#17: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and contains additional
oxygen-containing rings that having at least one additional Oxygen
Atom constitute O binding sites. Can include other Binding Site in
a Separate Ring (O ring systems bound to the O-containing
Monodentates, O--O Bidentates, O heterocyclic rings, but they do
not coordinate Tridentates, O Tetradentates, or O with the
stabilized, high valence metal ion. Hexadentates) Ring(s) can also
contain O, S, or P atoms. This 6-membered ring(s) and/or additional
O- containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. O Valence Stabilizer
#18: Macrocyclic ligands containing four, five, six, Four-, Five-,
Six-, Seven-, Eight-, and Ten- seven, eight, or ten oxygen binding
sites to Membered Macrocyclics, Macrobicyclics, valence stabilize
the central metal ion. Can and Macropolycyclics (including include
other hydrocarbon or ring systems Catapinands, Cryptands,
Cyclidenes, and bound to this macrocyclic ligand, but they do
Sepulchrates) wherein all Binding Sites are not coordinate with the
stabilized, high valence composed of Oxygen (usually ester or metal
ion. This ligand and/or attached, hydroxyl groups) and are not
contained in uncoordinating hydrocarbons/rings may or may Component
Heterocyclic Rings (O--O not have halogen or polarizing or water-
Bidentates, O--O Tridentates, O--O insolubilizing/solubiliz- ing
groups attached. Tetradentates, and O--O Hexadentates) O Valence
Stabilizer #19: Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, and Ten- five, six, seven,
eight, or ten five-membered Membered Macrocyclics, Macrobicyclics,
heterocyclic rings containing oxygen binding and Macropolycyclics
(including sites. Can include other hydrocarbon or ring
Catapinands, Cryptands, Cyclidenes, and systems bound to this
macrocyclic ligand, but Sepulchrates) wherein all Binding Sites are
they do not coordinate with the stabilized, high composed of Oxygen
and are contained in valence metal ion. This ligand and/or
attached, Component 5-Membered Heterocyclic uncoordinating
hydrocarbons/rings may or may Rings (O--O Bidentates, O--O
Tridentates, not have halogen or polarizing or water- O--O
Tetradentates, and O--O Hexadentates) insolubilizing/solubilizing
groups attached. O Valence Stabilizer #20: Macrocyclic ligands
containing a total of four, Four-, Five-, Six-, Seven-, Eight-, and
Ten- five, six, seven, eight, or ten six-membered Membered
Macrocyclics, Macrobicyclics, heterocyclic rings containing oxygen
binding and Macropolycyclics (including sites. Can include other
hydrocarbon or ring Catapinands, Cryptands, Cyclidenes, and systems
bound to this macrocyclic ligand, but Sepulchrates) wherein all
Binding Sites are they do not coordinate with the stabilized, high
composed of Oxygen and are contained in valence metal ion. This
ligand and/or attached, Component 6-Membered Heterocyclic
uncoordinating hydrocarbons/rings may or may Rings (O--O
Bidentates, O--O Tridentates, not have halogen or polarizing or
water- O--O Tetradentates, and O--O Hexadentates)
insolubilizing/solubilizing groups attached. N--S Valence
Stabilizer #1: RC(.dbd.NH)SR', where R and R' represent H or
Thioimidates, Dithioimidates, any organic functional group wherein
the Polythioimidates, and Derivatives of number of carbon atoms
ranges from 0 to 40, Thioimidic Acid (N--S Bidentates and N--S
optionally having halogen or polarizing or Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #2:
RR'--N--C(.dbd.NH)--NR"--CS--NR"'R"" for Thioguanylureas,
Guanidinothioureas, thioguanylureas, and
RR'--N--C(.dbd.NH)--NR"--NH-- Bis(thioguanylureas), CS--NR"'R"" for
guanidinothioureas, where R, Bis(guanidinothioureas), R', R", R"',
and R"" represent H, NH.sub.2, or any Poly(thioguanylureas), and
organic functional group wherein the number of
Poly(guanidinothioureas) (N--S Bidentates carbon atoms ranges from
0 to 40, optionally and N--S Tetradentates) having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #3: RR'--N--C(.dbd.NH)--NR"--CS--R"' for N--
Amidinothioamides, Guanidinothioamides, amidinothioamides, or
RR'--N--C(.dbd.NH)-- Bis(amidinothioamides), CR"R"'--CS--N--R""R""'
for 2-- Bis(guanidinothioamides), amidinothioacetamides, and
RR'--N--C(.dbd.NH)-- Poly(amidinothioamides), and NR"--NH--CS--R"'
for guanidinothioamides, Poly(guanidinothioamides) (including both
where R, R', R", R"', R"", and R""' represent N-amidinothioamides
and 2- H, NH.sub.2 , or any organic functional group
amidinothioacetamides) (N--S Bidentates wherein the number of
carbon atoms ranges and N--S Tetradentates) from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #4:
R--C(.dbd.NH)--NR'--CS--R", where R, R', and R", Imidoylthioamides,
represent H or any organic functional group Bis(imidoylthioamides),
and wherein the number of carbon atoms ranges
Poly(imidoylthioamides) (N--S Bidentates from 0 to 40, optionally
having halogen or and N--S Tetradentates) polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #5:
RR'NCSNR"R"', where R, R', R", and R"' Thioureas, Bis(thioureas),
and represent H, NH.sub.2, or any organic functional
Poly(thioureas), including Thiourylene group wherein the number of
carbon atoms Complexes (N--S Bidentates, N--S ranges from 0 to 40,
optionally having halogen Tridentates, and N--S Tetradentates) or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #6: RCSNR'R", where R, R', and R" represent H,
Thiocarboxamides, Bis(thiocarboxamides), NH.sub.2, or any organic
functional group wherein and Poly(thiocarboxamides) (N--S the
number of carbon atoms ranges from 0 to Bidentates, N--S
Tridentates, and N--S 40, optionally having halogen or polarizing
or Tetradentates) water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #7: RR'--N--S(.dbd.NH)--N--R"R"', where R,
R', R", and Imidosulfurous Diamides and R"' represent H or any
organic functional group Bis(imidosulfurous diamides) (N--S wherein
the number of carbon atoms ranges Bidentates, N--S Tridentates, and
N--S from 0 to 40, optionally having halogen or Tetradentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #8: R--N.dbd.S.dbd.N--R', where R and R'
represent H or Sulfurdiimines, Bis(sulfurdiimines), and any organic
functional group wherein the Poly(sulfurdiimines) (N--S Bidentates,
N--S number of carbon atoms ranges from 0 to 40, Tridentates, and
N--S Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #9:
(NH.dbd.)PR(OR')(SR") for phosphonimidothioic Phosphonimidothioic
Acid, acid and (NH.dbd.)PR(SR')(SR") for Phosphonimidodithioic
Acid, phosphonimidodithioic acid, where R, R', and
Bis(Phosphonimidothioic acid); R" represent H or any organic
functional group Bis(Phosphonimidodithioic acid), and wherein the
number of carbon atoms ranges derivatives thereof (N--S Bidentates,
N--S from 0 to 40, optionally having halogen or Tetradentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #10: (S.dbd.)PR(--NR'R")(--NR"'R""), where R,
R', R", Phosphonothioic Diamides, R"', and R"" represent H or any
organic Bis(phosphonothioic diamides), and functional group wherein
the number of carbon Poly(phosphonothioic diamides) (N--S atoms
ranges from 0 to 40, optionally having Bidentates and N--S
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#11: (S.dbd.)PR(--NR'R")(--OR"') or (O.dbd.)PR(--NR'R")(--
Phosphonamidothioic Acid, SR"') for phosphonamidothioic acid,
(S.dbd.)PR(-- Phosphonamidimidodithioic Acid, NR'R")(--SR"') for
phosphonamidimidodithioic Bis(phosphonamidothioic acid), acid,
where R, R', R", and R"' represent H or Bis(phosphonamidimidodithi-
oic acid), any organic functional group wherein the
poly(phosphonamidothioic acid), and number of carbon atoms ranges
from 0 to 40, poly(phosphonamidimidodithioic acid), and optionally
having halogen or polarizing or derivatives thereof (N--S
Bidentates and N--S water-insolubilizing/solubilizing groups
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. N--S Valence Stabilizer #12:
R--C(.dbd.S)--CR'.dbd.CR"--NHR"', where R, R', R",
Beta-Aminothiones (N-Substituted 3- and R"' represent H, or any
organic functional amino-2-propenethioaldehyde- s), Bis(beta- group
wherein the number of carbon atoms aminothiones), and Poly(beta-
ranges from 0 to 40, optionally having halogen aminothiones) (N--S
Bidentates and N--S or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#13: RR'--N--C(.dbd.S)--CR".dbd.C(--NHR"')R"- " for 3-
3-Aminothioacrylamides (3-Amino-2- aminothioacrylamides, and
RR'--N--C(.dbd.S)-- thiopropenamides), 3,3-
CR".dbd.C(--NHR"')(--NR""R""') for 3,3- Diaminothioacrylamides,
Bis(3- diaminothioacrylamides, where R, R', R", R"',
aminothioacrylamides), Bis(3,3- R"", R""' represent H, NH.sub.2, or
any organic diaminoacrylamides), Poly(3- functional group wherein
the number of carbon aminothioacrylamides), and Poly(3,3- atoms
ranges from 0 to 40, optionally having diaminothioacrylamides)
(N--S Bidentates halogen or polarizing or water- and N--S
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #14: R--O--C(.dbd.S)--CR'.dbd.C(--NHR")R"' or
R--S--C(.dbd.S)-- 3-Aminothioacrylic Acids (3-Amino-2-
CR'.dbd.C(--NHR")R"' for 3-aminothioacrylic thiopropenoic acids),
3-Mercapto-3- acids, and
R--O--C(.dbd.S)--CR'.dbd.C(--NHR")(--S--R"') aminothioacrylic
acids, Bis(3- or R--S--C(.dbd.S)--CR'.dbd.C(--NHR")(-- -S--R"') for
3- aminothioacrylic acids), Bis(3-Hydroxy-3-
mercapto-3-aminothioacrylic acids, where R, aminothioacrylic
acids), Poly(3- R', R", and R"' represent H, NH.sub.2, or any
aminothioacrylic acids), and Poly(3- organic functional group
wherein the number of Hydroxy-3-aminothioacrylic acids), and carbon
atoms ranges from 0 to 40, optionally derivatives thereof (N--S
Bidentates and N--S having halogen or polarizing or water-
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #15: R--C(.dbd.S)--N.dbd.CHR', where R' represents an
N-Thioacyl Benzylidenimines, Bis(N- aromatic derivative (i.e.
--C.sub.6H.sub.5), and R represent thioacyl benzylidenimines), and
Poly(N- H, NH.sub.2, or any organic functional group thioacyl
benzylidenimines) (N--S Bidentates wherein the number of carbon
atoms ranges and N--S Tetradentates) from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #16: R--C(.dbd.S)--C(.dbd.NOH)--R',
where R and R' Thiocarbonyl oximes, Bis(thiocarbonyl represent H,
NH.sub.2, or any organic functional oximes), and Poly(thiocarbonyl
oximes) group wherein the number of carbon atoms (N--S Bidentates,
N--S Tridentates, and N--S ranges from 0 to 40, optionally having
halogen Tetradentates) or polarizing or water-
insolubilizing/solubiliz- ing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#17: R--CH(--SH)--C(.dbd.NOH)--R', where R, R', and R" Mercapto
oximes, Bis(mercapto oximes), represent H, NH.sub.2, or any organic
functional and Poly(mercapto oximes) (including 2- group wherein
the number of carbon atoms sulfur heterocyclic oximes) (N--S ranges
from 0 to 40, optionally having halogen Bidentates, N--S
Tridentates, N--S or polarizing or water- Tetradentates, and N--S
Hexadentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #18: o--(O.sub.2N--)(HS--)Ar, where Ar represents an
2-Nitrothiophenols (2-nitrobenzenethiols) aromatic group or
heterocyclic wherein the (N--S Bidentates) number of carbon atoms
ranges from 6 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#19: o--(NC--(CH.sub.2).sub.0-1)(HS--)Ar, where Ar represents
2-Nitrilothiophenols (N--S Bidentates) an aromatic group or
heterocyclic wherein the number of carbon atoms ranges from 6 to
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #20: R--C(.dbd.S)--NHNR'R", where R, R', and R"
Thiohydrazides, Bis(thiohydrazides), and represent H or any organic
functional group Poly(thiohydrazides) (N--S Bidentates and wherein
the number of carbon atoms ranges N--S Tetradentates) from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#21: RR'--N--C(.dbd.S)--NHNR"R"', where R, R', and R"
Thiosemicarbazides, represent H or any organic functional group
Bis(thiosemicarbazides), and wherein the number of carbon atoms
ranges Poly(thiosemicarbazides) (N--S Bidentates, from 0 to 40,
optionally having halogen or N--S Tetradentates, and N--S
Hexadentates) polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #22: Macrocyclic ligands containing
five, seven, or Five-, Seven-, or Nine-Membered nine binding sites
composed of nitrogen and Macrocyclics, Macrobicyclics, and sulfur
to valence stabilize the central metal ion. Macropolycyclics
(including Catapinands, Can include other hydrocarbon or ring
systems Cryptands, Cyclidenes, and Sepulchrates) bound to this
macrocyclic ligand, but they do wherein all Binding Sites are
composed of not coordinate with the stabilized, high valence
Nitrogen (usually amine or imine groups) or metal ion. This ligand
and/or attached, Sulfur (usually thiols, mercaptans, or
uncoordinating hydrocarbons/rings may or may thiocarbonyls) and are
not contained in not have halogen or polarizing or water- Component
Heterocyclic Rings (N--S insolubilizing/solubilizing groups
attached. Tridentates, N--S Tetradentates, and N--S Hexadentates)
N--S Valence Stabilizer #23: Macrocyclic ligands containing a total
of five or Five-, or Seven-Membered Macrocyclics, seven
heterocyclic rings containing nitrogen or Macrobicyclics, and
Macropolycyclics sulfur binding sites. Can include other (including
Catapinands, Cryptands, hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but
they do not coordinate Binding Sites are composed of Nitrogen or
with the stabilized, high valence metal ion. This Sulfur and are
contained in Component ligand and/or attached, uncoordinating
Heterocyclic Rings (N--S Tridentates, N--S hydrocarbon/rings may or
may not have halogen Tetradentates, or N--S Hexadentates) or
polarizing or water-insolubilizing groups attached. N--S Valence
Stabilizer #24: Macrocyclic ligands containing at least one Five-,
Seven-, or Nine-Membered heterocyclic ring. These heterocyclic
rings Macrocyclics, Macrobicyclics, and provide nitrogen or sulfur
binding sites to Macropolycyclics (including Catapinands, valence
stabilize the central metal ion. Other Cryptands, Cyclidenes, and
Sepulchrates) amine, imine, thiol, mercapto, or thiocarbonyl
wherein all Binding Sites are composed of binding sites can also be
included in the Nitrogen or Sulfur and are contained in a
macrocyclic ligand, so long as the total number Combination of
Heterocyclic Rings and of binding sites is five, seven, or nine.
Can Amine, Imine, Thiol, Mercapto, or include other
hydrocarbon/ring systems bound Thiocarbonyl Groups (N--S
Tridentates, N--S to this macrocyclic ligand, but they do not
Tetradentates, or N--S Hexadentates) coordinate with the
stabilized, high valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. N--O Valence
Stabilizer #1: RC(.dbd.NH)OR', where R and R' represent H or
Imidates, Diimidates, Polyimidates, and any organic functional
group wherein the Derivatives of Imidic Acid (N--O Bidentates
number of carbon atoms ranges from 0 to 40, and N--O Tetradentates)
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #2:
RR'NC(.dbd.NH)OR", where R, R', and R" Pseudoureas,
bis(pseudoureas), and represent H, NH.sub.2, or any organic
functional poly(pseudoureas) (N--O Bidentates and N-- group wherein
the number of carbon atoms O Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #3:
RR'NC(.dbd.NH)CR"R"'(CO)OR"", where R, R', 2-Amidinoacetates,
Bis(2-amidinoacetates), R", R"', and R"" represent H, NH.sub.2, or
any and Poly(2-amidinoacetates) (N--O organic functional group
wherein the number of Bidentates and N--O Tetradentates) carbon
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water- insolubilizing/solubilizin- g groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #4: RR'NCONR"R"', where R, R', R", and R"' Ureas,
Bis(ureas), and Poly(ureas), represent H, NH.sub.2, or any organic
functional including Urylene Complexes (N--O group wherein the
number of carbon atoms Bidentates, N--O Tridentates, and N--O
ranges from 0 to 40, optionally having halogen Tetradentates) or
polarizing or water- insolubilizing/solubiliz- ing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #5: (NH.dbd.)PR(OR')(OR"), where R, R', and R"
Phosphonimidic Acid, Bis(phosphonimidic represent H, NH.sub.2, or
any organic functional acid), Poly(phosphonimidic acid), and group
wherein the number of carbon atoms derivatives thereof (N--O
Bidentates and N-- ranges from 0 to 40, optionally having halogen O
Tetradentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms N--O Valence Stabilizer #6: (O.dbd.)PR(--NR'R")(--OR"') for
phosphonamidic Phosphonamidic Acid, Phosphonic acid and
(O.dbd.)PR(--NR'R")(--NR"'R"") for Diamide, Bis(Phosphonamidic
Acid), phosphonic diamide, where R, R', R", R"', and Bis(Phosphonic
Diamide), R"" represent H, NH.sub.2, or any organic functional
Poly(phosphonamidic acid), group wherein the number of carbon atoms
poly(phosphonic diamide), and derivatives ranges from 0 to 40,
optionally having halogen thereof (N--O Bidentates and N--O or
polarizing or water- Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #7:
R--C(.dbd.O)--CR'.dbd.C(--NHR")R"', where R, R', R",
Beta-Ketoamines (N-Substituted 3-amino- and R"' represent H, or any
organic functional 2-propenals), Bis(beta-ketoamines), and group
wherein the number of carbon atoms Poly(beta-ketoamines) (N--O
Bidentates and ranges from 0 to 40, optionally having halogen N--O
Tetradentates) or polarizing or water- insolubilizing/solubilizin-
g groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #8: RR'
--N--C(.dbd.O)--CR".dbd.C(--NHR"')R"" for 3- 3-Aminoacrylamides
(3-Amino-2- aminoacrylamides, and RR'--N--C(.dbd.O)--CR".dbd.C(--
propenamides), 3,3-Diaminoacrylamides, NHR"')(--NR""R""') for 3,3-
Bis(3-aminoacrylamides), Bis(3,3- diaminoacrylamides, where R, R',
R", R"', R"", diaminoacrylamides), Poly(3- and R""' represent H,
NH.sub.2, or any organic aminoacrylamides), and Poly(3,3-
functional group wherein the number of carbon diaminoacrylamides)
(N--O Bidentates and atoms ranges from 0 to 40, optionally having
N--O Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #9:
R--O--C(.dbd.O)--CR'.dbd.C(--NHR")R"' for 3- 3-Aminoacrylic Acids
(3-Amino-2- aminoacrylic acids, and R--O--C(.dbd.O)--CR'.dbd.C(--
propenoic acids), 3-Hydroxy-3- NHR")(--O--R"') for
3-hydroxy-3-aminoacrylic aminoacrylic acids, Bis(3-aminoacrylic
acids, where R, R', R", and R"' represent H, acids),
Bis(3-Hydroxy-3-aminoacrylic NH.sub.2, or any organic functional
group wherein acids), Poly(3-aminoacrylic acids), and the number of
carbon atoms ranges from 0 to Poly(3-Hydroxy-3-aminoacrylic acids),
and 40, optionally having halogen or polarizing or derivatives
thereof (N--O Bidentates and N-- water-insolubilizing/solubil-
izing groups O Tetradentates) attached. Ligand can also contain
nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #10:
R--C(.dbd.O)--N.dbd.CHR', where R' represents an N-Acyl
Benzylidenimines, Bis(N-acyl aromatic derivative (i.e.
--C.sub.6H.sub.5), and R represent benzylidenimines), and
Poly(N-acyl H, NH.sub.2, or any organic functional group
benzylidenimines) (N--O Bidentates and N-- wherein the number of
carbon atoms ranges O Tetradentates) from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #11: o--(O.sub.2N--)(RR'N--)Ar,
where Ar represents an 2-Nitroanilines (N--O Bidentates) aromatic
group or heterocyclic wherein the number of carbon atoms ranges
from 6 to 40, and R and R' represent H, NH2, or alkyl or aryl
hydrocarbon groups wherein the number of carbon atoms range from 0
to 25, optionally having halogen or polarizing or water-
insolubilizing/solubilizin- g groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#12: o--(NC--(CH.sub.2).sub.0-1)(HO--)Ar, where Ar represents
2-Nitrilophenols (N--O Bidentates). Also an aromatic group or
heterocyclic wherein the includes acylcyanamides. number of carbon
atoms ranges from 6 to 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #13: Het N.sup.+--O.sup.-for amine N--oxides, and
R--N.dbd.N.sup.+(--O.sup.-)-- Amine N--Oxides and Diazine N--Oxides
R' for diazine N--oxides (azoxy compounds), (Azoxy componds) (N--O
Bidentates, N--O where Het represents a nitrogen-containing
Tridentates, and N--O Tetradentates) heterocyclic derivative
wherein the number of carbon atoms ranges from 4 to 40, and R and
R' represent separate or the same aromatic functionalities, both
Het and R,R' optionally having halogen or polarizing or water-
insolubilizing/solubilizin- g groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#14: R--C(.dbd.O)--NHNR'R", where R, R', and R" Hydrazides,
Bis(hydrazides), and represent H or any organic functional group
Poly(hydrazides) (N--O Bidentates and N--O wherein the number of
carbon atoms ranges Tetradentates) from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #15: RR'--N--C(.dbd.O)--NHNR"R"', where R,
R', and R" Semicarbazides, Bis(semicarbazides), and represent H or
any organic functional group Poly(semicarbazides) (N--O Bidentates,
N--O wherein the number of carbon atoms ranges Tetradentates, and
N--O Hexadentates) from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #16: Macrocyclic ligands containing five, seven,
or Five-, Seven-, or Nine-Membered nine binding sites composed of
nitrogen and Macrocyclics, Macrobicyclics, and oxygen to valence
stabilize the central metal Macropolycyclics (including
Catapinands, ion. Can include other hydrocarbon or ring Cryptands,
Cyclidenes, and Sepulchrates) systems bound to this macrocyclic
ligand, but wherein all Binding Sites are composed of they do not
coordinate with the stabilized, high Nitrogen (usually amine or
imine groups) or valence metal ion. This ligand and/or attached,
Oxygen (usually hydroxy, carboxy, or uncoordinating
hydrocarbons/rings may or may carbonyl groups) and are not
contained in not have halogen or polarizing or water- Component
Heterocyclic Rings (N--O insolubilizing/solubilizing groups
attached. Tridentates, N--O Tetradentates, and N--O Hexadentates)
N--O Valence Stabilizer #17: Macrocyclic ligands containing a total
of five or Five-, or Seven-Membered Macrocyclics, seven
heterocyclic rings containing nitrogen or Macrobicyclics, and
Macropolycyclics oxygen binding sites. Can include other (including
Catapinands, Cryptands, hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but
they do not coordinate Binding Sites are composed of Nitrogen or
with the stabilized, high valence metal ion. This Oxygen and are
contained in Component ligand and/or attached, uncoordinating
Heterocyclic Rings (N--O Tridentates, N--O hydrocarbon/rings may or
may not have halogen Tetradentates, or N--O Hexadentates) or
polarizing or water-insolubilizing groups attached. N--O Valence
Stabilizer #18: Macrocyclic ligands containing at least one Five-,
Seven-, or Nine-Membered heterocyclic ring. These heterocyclic
rings Macrocyclics, Macrobicyclics, and provide nitrogen or oxygen
binding sites to Macropolycyclics (including Catapinands, valence
stabilize the central metal ion. Other Cryptands, Cyclidenes, and
Sepulchrates) amine, imine, hydroxy, carboxy, or carbonyl wherein
all Binding Sites are composed of binding sites can also be
included in the Nitrogen or Oxygen and are contained in a
macrocyclic ligand, so long as the total number Combination of
Heterocyclic Rings and of binding sites is five, seven, or nine.
Can Amine, Imine, Hydroxy, Carboxy, or include other
hydrocarbon/ring systems bound Carbonyl Groups (N--O Tridentates,
N--O to this macrocyclic ligand, but they do not Tetradentates, or
N--O Hexadentates) coordinate with the stabilized, high valence
metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. S--O Valence Stabilizer #1:
RR'--N--C(.dbd.S)--NR"--C(.dbd.O)--NR"'R"" for Thiobiurets
(Thioimidodicarbonic thiobiurets, and
RR'--N--C(.dbd.S)--NR"--NH--C(.dbd.O)-- Diamides), Thioisobiurets,
Thiobiureas, NR"'R"" for thiobiureas, where R, R', R", R"',
Thiotriurets, Thiotriureas, Bis(thiobiurets), and R"" represent H,
NH.sub.2, or any organic Bis(thioisobiurets), Bis(thiobiureas),
functional group wherein the number of carbon Poly(thiobiurets),
Poly(thioisobiurets), atoms ranges from 0 to 40, optionally having
Poly(thiobiureas) (S--O Bidentates, S--O halogen or polarizing or
water- Tridentates, S--O Tetradentates), and (3-
insolubilizing/solubiliz- ing groups attached. formamidino
thiocarbamides) Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #2:
RR'--N--C(.dbd.S)--NR"--C(.dbd.O)--R"' for acyl--and Acylthioureas,
Aroylthioureas, aroylthioureas, and
RR'--N--C(.dbd.O)--NR"--C(.dbd.S)-- Thioacylureas, Thioaroylureas,
R"'for thioacyl--and thioaroylureas, where R, Bis(acylthioureas),
Bis(aroylthioureas), R', R", and R"' represent H, NH.sub.2, or any
Bis(thioacylureas), Bis(thioaroylureas), organic functional group
wherein the number of Poly(thioacylthioureas), carbon atoms ranges
from 0 to 40, optionally Poly(thioaroylthioureas), having halogen
or polarizing or water- Poly(thioacylureas), and
insolubilizing/solubilizing groups attached. Poly(thioaroylureas)
(S--O Bidentates, S--O Ligand can also contain nonbinding N, O, S,
or Tridentates, S--O Tetradentates) P atoms. S--O Valence
Stabilizer #3: RC(.dbd.S)--NR'--C(.dbd.O)--R" for
Thioimidodialdehydes, thioimidodialdehydes, and
RC(.dbd.S)--NR'--NH--
Thiohydrazidodialdehydes (thioacyl C(.dbd.O)--R" for
thiohydrazidodialdehydes hydrazides), Bis(thioimidodialdehydes),
(thioacyl hydrazides), where R, R', and R" Bis(thiohydrazidodialde-
hydes), represent H, NH.sub.2, or any organic functional
Poly(thioimidodialdehydes), and group wherein the number of carbon
atoms Poly(thiohydrazidodialdehydes) (S--O ranges from 0 to 40,
optionally having halogen Bidentates, S--O Tridentates, S--O or
polarizing or water- Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #4: R--O--C(.dbd.S)--NR'--C-
(.dbd.O)--O--R"or R--S--C(.dbd.S)-- Thioimidodicarbonic acids,
NR'--C(.dbd.O)--S--R" for thioimidodicarbonic acids,
Thiohydrazidodicarbonic acids, and
R--O--C(.dbd.S)--NR'--NH--C(.dbd.O)--O- --R" or R--S--
Bis(thioimidodicarbonic acids),
C(.dbd.S)--NR'--NH--C(.dbd.O)--S--R" for Bis(thiohydrazidodicarbon-
ic acids), thiohydrazidodicarbonic acids, where R, R', and
Poly(thioimidodicarbonic acids), R" represent H, NH.sub.2, or any
organic functional Poly(thiohydrazidodicarbonic acids) and group
wherein the number of carbon atoms derivatives thereof (S--O
Bidentates, S--O ranges from 0 to 40, optionally having halogen
Tridentates, S--O Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #5:
R--C(.dbd.S)--C(.dbd.O)--R' where R and R' represent H,
1,2-Monothioketones (Monothiolenes, NH.sub.2, or any organic
functional group wherein Monothio--alpha--ketonates), 1,2,3- the
number of carbon atoms ranges from 0 to Monothioketones,
1,2,3-Dithioketones, 40, optionally having halogen or polarizing or
Monothiotropolonates, ortho- water-insolubilizing/solubilizing
groups Monothioquinones, Bis(1,2- attached. Ligand can also contain
nonbinding N, Monothioketones), and Poly(1,2- O, S, or P atoms.
Monothioketones) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) S--O Valence Stabilizer #6: RR'--N--C(.dbd.S)--S--S-
--C(.dbd.O)--N--R"R"' for Trithioperoxydicarbonic Diamides,
trithioperoxydicarbonic diamides, and RR'--N--
Dithioperoxydicarbonic Diamides,
C(.dbd.O)--S--S--C(.dbd.O)--N--R"R"' for
Bis(trithioperoxydicarbonic diamides), dithioperoxydicarbonic
diamides, where R, R', Bis(dithioperoxydicarbonic diamides), R",
R"' represent H or any organic functional poly(trithioperoxydicarb-
onic diamides) and group wherein the number of carbon atoms
poly(dithioperoxydicarbonic diamides) (S--O ranges from 0 to 40,
optionally having halogen Bidentates, S--O Tridentates, S--O or
polarizing or water- Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #7: R--O--C(.dbd.S)--S--C(.-
dbd.O)--O--R', where R and R' Diithiodicarbonic Acids, represent H,
NH.sub.2 or any organic functional Bis(dithiodicarbonic acids),
group wherein the number of carbon atoms Poly(dithiodicarbonic
acids), and ranges from 0 to 40, optionally having halogen
derivatives thereof (S--O Bidentates, S--O or polarizing or water-
Tridentates, S--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #8: R--O--C(.dbd.S)--S--S--C(.dbd-
.O)--O--R', where R and R' Trithioperoxydicarbonic Acids, represent
H, NH.sub.2 or any organic functional Bis(trithioperoxydicarbonic
acids), group wherein the number of carbon atoms
poly(trithioperoxydicarbonic acids), and ranges from 0 to 40,
optionally having halogen derivatives thereof (S--O Bidentates,
S--O or polarizing or water- Tridentates, S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #9:
(RR'--N--)(R"R"'--N--)P(.dbd.S)--S--S--P(.dbd.O)(--N--
Monothioperoxydiphosphoramide, R""R""')(--N--R"""R"""'), where R,
R', R", R"', Bis(monothioperoxyphosphoramide), and R"", R""', R""",
and R"""' represent H, NH.sub.2 or Poly(monothioperoxydiphosphoram-
ide) (S--O any organic functional group wherein the Bidentates,
S--O Tridentates, S--O number of carbon atoms ranges from 0 to 40,
Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#10: (R--O--)(R'--O--)P(.dbd.S)--S--S--P(.dbd.O)(--O--R")(--O-- -
Monothioperoxydiphosphoric Acids, R"'); (R--O--)(R'--S--)P(.dbd.S-
)--S--S--P(.dbd.O)(--S--R")(-- Bis(monothioperoxyphosphoric Acids),
O--R"'); or (R--S--)(R'--S--)P(.dbd.S)--S--S--P(.dbd.O)(--S--
Poly(monothioperoxydiphosphoric Acids), R")(--S--R"'), where R, R',
R", R"', R"", R""', and derivatives thereof (S--O Bidentates, S--O
R""", and R"""' represent H, NH.sub.2or any Tridentates, S--O
Tetradentates) organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #11: (R--O--)(R'--)P(.dbd.S)--NH--P(.dbd.O)(-
--R")(--O--R"'); (R-- Monothioimidodiphosphonic Acids,
S--)(R'--)P(.dbd.S)--NH--P(.dbd.O)(--R")(--O--R"'); or (R--
Monothiohydrazidodiphosphonic Acids,
S--)(R'--)P(.dbd.S)--NH--P(.dbd.O)(-- -R")(--S--R"') for
Bis(monothioimidodiphosphonic Acids), monothioimidodiphosphonic
acids, and --NH-- Bis(monothiohydrazidodiphosphonic NH--derivatives
for Acids), Poly(monothioimidodiphosphonic
monothiohydrazidodiphosphonic acids, where Acid), R, R', R", and
R"' represent H, NH.sub.2or any Poly(monothiohydrazidodiphosphonic
organic functional group wherein the number of Acids), and
derivatives thereof (S--O carbon atoms ranges from 0 to 40,
optionally Bidentates, S--O Tridentates, S--O having halogen or
polarizing or water- Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #12:
(RR'--N--)(R"--)P(.dbd.S)--NH--P(.dbd.O)(--R"')(--N--
Monothioimidodiphosphonamides, R""R""') for
monothioimidodiphosphonami- des, Monothiohydrazidodiphosphonamides,
and --NH--NH--derivatives for Bis(monothioimidodiphosphonamides),
monothiohydrazidodiphospho- namides, where R,
Bis(monothiohydrazidodiphosphonamidcs) R', R", R"', R"", and R""',
represent H, NH.sub.2or Poly(monothioimidodiphosphonamides), any
organic functional group wherein the and number of carbon atoms
ranges from 0 to 40, Poly(monothiohydrazidodiphosphonamides)
optionally having halogen or polarizing or (S--O Bidentates, S--O
Tridentates, S--O water-insolubilizing/solubilizing groups
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. S--O Valence Stabilizer #13:
(RR'--N--)(R"--)P(.dbd.S)--S--P(.dbd.O)(--R"- ')(--N--
Monothiodiphosphonamides, R""R""'), or
(RR'--N--)(R"--)P(.dbd.S)--O--P(.dbd.O)(-- Bis(monothioiphosphonar-
nides), and R"')(--N--R""R""'), where R, R', R", R"', R"",
Poly(monothiodiphosphonamides) (S--O and R""' represent H,
NH.sub.2or any organic Bidentates, S--O Tridentates, S--O
functional group wherein the number of carbon Tetradentates) atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#14: (R--O--)(R'--)P(.dbd.S)--O--P(.dbd.O)(--R")(--O--R"'); (R--
Monothiodiphosphonic Acids, O--)(R'--)P(.dbd.S)--S--P(.dbd.O)-
(--R")(--O--R"'); (R--S--) Bis(monothioiphosphonic Acids),
(R'--)P(.dbd.S)--O--P(.dbd.O)(--R")(--S--R"'); or (R--S--)
Poly(monothiodiphosphonic Acids), and
(R'--)P(.dbd.S)--S--P(.dbd.O)(--R")- (--S--R"'), where R,
derivatives thereof (S--O Bidentates, S--O R', R", and R"'
represent H, NH.sub.2or any organic Tridentates, S--O
Tetradentates) functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#15: (RR'--N--)(R"--)P(.dbd.S)--S--S--P(.dbd- .O)(--R"')(--N--
Monothioperoxydiphosphonamide, R""R""'), where R, R', R", R"', R"",
and R""' Bis(monothioperoxyphosphonamide), and represent H,
NH.sub.2 or any organic functional
Poly(monothioperoxydiphosphonamide) (S--O group wherein the number
of carbon atoms Bidentates, S--O Tridentates, S--O ranges from 0 to
40, optionally having halogen Tetradentates) or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#16: (R--O--)(R'--)P(.dbd.S)--S--S--P(.dbd.O)(--R- ")(--O--R"'); or
Monothioperoxydiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--S--S--P(.dbd.O)(--R")(--S--R"'),
Bis(monothioperoxyphosphonic Acids), where R, R', R", and R"'
represent H, NH.sub.2 or Poly(monothioperoxydiphosphonic Acids),
any organic functional group wherein the and derivatives thereof
(S--O Bidentates, S--O number of carbon atoms ranges from 0 to 40,
Tridentates, S--O Tetradentates) optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #17: (O.dbd.)P(--S--R)(--O--R')(--O--R") or
(S.dbd.)P(--O--R)(--O-- Monothiophosphoric Acids R')(--O--R"),
where R, R', and R" represent H, (Phosphorothioic Acids),
NH.sub.2or any organic functional group wherein
Bis(monothiophosphoric acids), the number of carbon atoms ranges
from 0 to Poly(monothiophosphoric acids), and 40, optionally having
halogen or polarizing or derivatives thereof (S--O Bidentates, S--O
water-insolubilizing/solubilizing groups Tridentates, S--O
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. S--O Valence Stabilizer #18:
(O.dbd.)P(--S--S--R)(--O--R')(--O--R"), where R, R',
Phosphoro(dithioperoxoic) Acids, and R" represent H, NH.sub.2 or
any organic Bis[phosphoro(dithioperoxoic) acids], functional group
wherein the number of carbon Poly[phosphoro(dithioperoxoic) acids],
and atoms ranges from 0 to 40, optionally having derivatives
thereof (S--O Bidentates, S--O halogen or polarizing or water-
Tridentates, S--O Tetradentates) insolubilizing/solubilizin- g
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #19: (O.dbd.)PR(--S--R')(--O--R") or
(S.dbd.)PR(--O--R')(--O-- Monothiophosphonic Acids R"), where R,
R', and R" represent H, NH.sub.2 or (Phosphonothioic Acids), any
organic functional group wherein the Bis(monothiophosphonic Acids),
number of carbon atoms ranges from 0 to 40, Poly(monothiophosphonic
Acids), and optionally having halogen or polarizing or derivatives
thereof (S--O Bidentates, S--O water-insolubilizing/solubilizing
groups Tridentates, S--O Tetradentates) attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#20: (O.dbd.)PR(--S--S--R')(--O--R"), where R, R', and R"
Phosphono(dithioperoxoic) Acids, represent H, NH.sub.2 or any
organic functional Bis[phosphono(dithioperoxoic) Acids], group
wherein the number of carbon atoms Poly[phosphono(dithioperoxoic)
Acids], ranges from 0 to 40, optionally having halogen and
derivatives thereof (S--O Bidentates, S--O or polarizing or water-
Tridentates, S--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #21: R--CR'(--OH)--CH2--C(.dbd.S)- --R",
where R, R', and Beta-Hydroxythioketones, Beta- R" represent H,
NH.sub.2 or any organic functional Hydroxythioaldehydes, Bis(beta-
group wherein the number of carbon atoms hydroxythioketones),
Bis(beta- ranges from 0 to 40, optionally having halogen
hydroxythioaldehydes), Poly(beta- or polarizing or water-
hydroxythioketones), and Poly(beta- insolubilizing/solubilizing
groups attached. hydroxythioaldehydes) (S--O Bidentates, S--O
Ligand can also contain nonbinding N, O, S, or Tridentates, S--O
Tetradentates) P atoms. S--O Valence Stabilizer #22:
R--CR'(--SH)--CH2--C(.dbd.O)--R", where R, R', and
Beta-Mercaptoketones, Beta- R" represent H, NH.sub.2 or any organic
functional Mercaptoaldehydes, Bis(beta- group wherein the number of
carbon atoms mercaptoketones), Bis(beta- ranges from 0 to 40,
optionally having halogen mercaptoaldehydes), Poly(beta- or
polarizing or water- mereaptoketones), and Poly(beta-
insolubilizing/solubilizing groups attached. mercaptoaldehydes)
(S--O Bidentates, S--O Ligand can also contain nonbinding N, O, S,
or Tridentates, S--O Tetradentates) P atoms. S--O Valence
Stabilizer #23: RR'--N--CH(--OH)--NR"--C(.dbd.S)--NR"'R"", where
N-(Aminomethylol)thioureas [N- R, R', R", R"', and R"" represent H,
NH.sub.2 or any (Aminohydroxymethyl)thioureas], Bis[N- organic
functional group wherein the number of (aminomethylol)thioureas],
and Poly[N- carbon atoms ranges from 0 to 40, optionally
(aminomethylol)thioureas](S--O Bidentates, having halogen or
polarizing or water- S--O Tridentates, S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#24: RR'--N--CH(--SH)--NR"--C(.dbd.O)--NR"'R"", where
N-(Aminomethylthiol)ureas [N- R, R', R", R"', and R"" represent H,
NH.sub.2 or any (Aminomercaptomethyl)ureas], Bis[N- organic
functional group wherein the number of (aminomethylthiol)ureas],
and Poly[N- carbon atoms ranges from 0 to 40, optionally
(aminomethylthiol)ureas](S--O Bidentates, having halogen or
polarizing or water- S--O Tridentates, S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#25: RR'--N--C(.dbd.S)--C(.dbd.O)--N--R"R"', where R, R',
Monothiooxamides, R", and R"' represent H, NH.sub.2 or any organic
Bis(monothiooxamides), and functional group wherein the number of
carbon Poly(monothiooxamides) (S--O Bidentates, atoms ranges from 0
to 40, optionally having S--O Tridentates, S--O Tetradentates)
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #26:
R--CR'(--SH)--CR"R"'--C(.dbd.O)(--O--R""), where R, Beta-Mercapto
Carboxylic Acids, Bis(Beta- R', R", R"', and R"" represent H,
NH.sub.2 or any Mercapto Carboxylic Acids), Poly(Beta- organic
functional group wherein the number of Mercapto Carboxylic Acids),
and carbon atoms ranges from 0 to 40, optionally derivatives
thereof (S--O Bidentates, S--O having halogen or polarizing or
water- Tridentates, S--O Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #27: R--CR'(--SH)--CR"R"'--C(.dbd-
.O)(--S--R""), where R, Beta-Mercapto Thiocarboxylic Acids, R', R",
R"', and R"" represent H, NH.sub.2 or any Bis(Beta-Mercapto
Thiocarboxylic Acids), organic functional group wherein the number
of Poly(Beta-Mercapto Thiocarboxylic Acids), carbon atoms ranges
from 0 to 40, optionally and derivatives thereof (S--O Bidentates,
S--O having halogen or polarizing or water- Tridentates, S--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #28: R--CR'(--OH)--CR"R"'--C(.dbd.O)(--S--R""), where R,
Beta-Hydroxy Thiocarboxylic Acids, R', R", R"', and R"" represent
H, NH.sub.2 or any Bis(Beta-Hydroxy Thiocarboxylic Acids), organic
functional group wherein the number of Poly(Beta-Hydroxy
Thiocarboxylic Acids), carbon atoms ranges from 0 to
40, optionally and derivatives thereof (S--O Bidentates, S--O
having halogen or polarizing or water- Tridentates, S--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #29: R--CR'(--SH)--CR"R"'--C(.dbd.O)(--NH--R""), where
Beta-Mercapto Carboxamides, Bis(Beta- R, R', R", R"', and R""
represent H, NH.sub.2 or any Mercapto Carboxamides), Poly(Beta-
organic functional group wherein the number of Mercapto
Carboxamides), and derivatives carbon atoms ranges from 0 to 40,
optionally thereof (S--O Bidentates, S--O Tridentates, having
halogen or polarizing or water- S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#30: R--S--R'COOH for S-alkylthiocarboxylic and S-
S-Alkylthiocarboxylic Acids, S- arylthiocarboxylic acids, and
HOOCR--S-- Arylthiocarboxylic Acids, and S,S- R'COOH for
S,S-thiobiscarboxylic acids, where thiobiscarboxylic Acids (S--O
Bidentates R and R' represent H or any organic functional and S--O
Tridentates) group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#31: R--S--S--R'COOH for S-alkyldisulfidocarboxylic
S-Alkyldisulfidocarboxylic Acids, S- and S-aryldisulfidocarboxylic
acids, and Aryldisulfidocarboxylic Acids, and S,S'--
HOOCR--S--S--R'COOH for S,S'- Disulfidobiscarboxylic Acids (S--O
disulfidobiscarboxylic acids, where R and R' Bidentates and S--O
Tridentates) represent H or any organic functional group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #32: R--C(.dbd.O)(--S--R') for
monothiomonocarboxylic Monothiomonocarboxylic Acids, acids, and
(R--S--)(O.dbd.)C--R'--C(.dbd.O)(--S--R") or (R--
Dithiodicarboxylic Acids, S--)(O.dbd.)C--R'--C(.dbd.O)(--O--R") for
Bis(monothiomonocarboxylic Acids), dithiodicarboxylic acids, where
R, R', and R" Bis(dithiodicarboxylic acids), represent H, NH.sub.2
or any organic functional Poly(monothiomonocarboxylic acids), group
wherein the number of carbon atoms Poly(dithiodicarboxylic acids),
and ranges from 0 to 40, optionally having halogen derivatives
thereof (S--O Bidentates and S--O or polarizing or water-
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #33: R--O--C(.dbd.S)--O--R', where R, and R' represent
H, Monothiocarbonates and NH.sub.2 or any organic functional group
wherein Bis(monothiocarbonates) (S--O Bidentates the number of
carbon atoms ranges from 0 to and S--O Tetradentates) 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#34: RR'N--NR"--C(.dbd.O)(SH), where R and R' Monothiocarbazates
(Monothiocarbazides), represent H, NH.sub.2 or any organic
functional Bis(monothiocarbazates), and group wherein the number of
carbon atoms Poly(monothiocarbazates) (S--O Bidentates, ranges from
0 to 40, optionally having halogen S--O Tridentates, and S--O
Tetradentates; or or polarizing or water- possibly N--S Bidentates,
N--S Tridentates, insolubilizing/solubilizing groups attached. and
N--S Tetradentates) Ligand can also contain nonbinding N, O, S, or
P atoms. S--O Valence Stabilizer #35: R--CH(--SH)--CH(--OH)--R' for
alpha-mercapto Mercapto Alcohols and alcohols,
R--CH(--SH)--Si(--OR').sub.x--R".sub.3-x for alpha-
Silylmercaptoalcohols, Bis(mercapto silylmercaptoalcohols,
R--CH(--SH)--R'--CH(-- alcohols and silylmercaptoalcohols), and
OH)--R" for beta-mercapto alcohols, and R--CH(-- Poly(mercapto
alcohols and SH)--R'--Si(--OR").sub.x--R"'.sub.3-x for beta-
silylmercaptoalcohols) (S--O Bidentates, S--O
silylmercaptoalcohols, etc., where R, R', R", Tridentates, S--O
Tetradentates) and R"' represent H, NH.sub.2 or any organic
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. x = 1-3. Ligand can
also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #36: RN.dbd.C(OH)(SH), where R represents H, NH.sub.2 or
Monothiocarbimates, any organic functional group wherein the
Bis(monothiocarbimates), and number of carbon atoms ranges from 0
to 40, Poly(monothiocarbimates) (S--O Bidentates, optionally having
halogen or polarizing or S--O Tridentates, and S--O Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#37: R--O--C(--S--R")--O--R', where R, R', and R" Alkyl-and
Aryl-Monothioborates and represent H, NH.sub.2 or any organic
functional Bis(monothioborates) (S--O Bidentates and group wherein
the number of carbon atoms S--O Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#38: R--C(--S--R")--O--R', where R, R', and R" Alkyl-and
Aryl-Monothioboronates and represent H, NH.sub.2 or any organic
functional Bis(monothioboronates) (S--O Bidentates group wherein
the number of carbon atoms and S--O Tetradentates) ranges from 0 to
40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#39: (O.dbd.)As(--S--R)(--O--R')(--O--R") or (S.dbd.)As(--O--
Monothioarsonic Acids (Arsonothioic R)(--O--R')(--O--R"), where R,
R', and R" Acids), Bis(monothioarsonic acids), represent H,
NH.sub.2 or any organic functional Poly(monothioarsonic acids), and
group wherein the number of carbon atoms derivatives thereof (S--O
Bidentates, S--O ranges from 0 to 40, optionally having halogen
Tridentates, S--O Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#40: Heterocyclic ring(s) containing one or two Heterocyclic Rings
containing One or Two sulfur atoms. In addition, ligand contains
Sulfur Atoms at least one additional additional oxygen-containing
substituents Oxygen Atom Binding Site not in a Ring (usually
hydroxy, carboxy, or carbonyl groups) (S--O Bidentates, S--O
Tridentates, S--O that constitute O binding sites. Can include
Tetradentates, or S--O Hexadentates) other ring systems bound to
the heterocyclic ring or to the O-containing substituent, but they
do not coordinate with the stabilized, high valence metal ion.
Ring(s) can also contain O, N, P, As or Se atoms. This 5-membered
ring(s) and/or attached, uncoordinating rings and/or O- containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #41: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two oxygen atoms. In addition,
ligand contains Oxygen Atoms at least one additional additional
sulfur-containing substituents Sulfur Atom Binding Site not in a
Ring (S--O (usually thio, mercapto, or thiocarbonyl groups)
Bidentates, S--O Tridentates, S--O that constitute S binding sites.
Can include Tetradentates, or S--O Hexadentates) other ring systems
bound to the heterocyclic ring or to the S-containing substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, N, P, As or Se atoms. This
5-membered ring(s) and/or attached, uncoordinating rings and/or S-
containing substituent(s) may or may not have halogen or polarizing
or water- insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #42: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two sulfur atoms. In addition,
ligand contains Sulfur Atoms at least one additional additional
oxygen-containing rings that Oxygen Atom Binding Site in a separate
constitute O binding sites. Can include other Ring (S--O
Bidentates, S--O Tridentates, S--O ring systems bound to the
O-containing Tetradentates, or S--O Hexadentates) heterocyclic
rings, but they do not coordinate with the stabilized, high valence
metal ion. Ring(s) can also contain O, N, P, As, or Se atoms. This
5-membered ring(s) and/or additional O-containing ring(s) and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
S--O Valence Stabilizer #43: Macrocyclic ligands containing two to
ten sulfur Two-, Three-, Four-, Five-, Six-, Seven-, or oxygen
binding sites to valence stabilize the Eight-, Nine-, and
Ten-Membered central metal ion. Can include other Macrocyclics,
Macrobicyclics, and hydrocarbon or ring systems bound to this
Macropolycyclics (including Catapinands, macrocyclic ligand, but
they do not coordinate Cryptands, Cyclidenes, and Sepulchrates)
with the stabilized, high valence metal ion. This wherein all
Binding Sites are composed of ligand and/or attached,
uncoordinating Sulfur (usually thiol, mercapto, or
hydrocarbons/rings may or may not have thiocarbonyl groups) or
Oxygen (hydroxy, halogen or polarizing or water- carboxy, or
carbonyl groups) and are not insolubilizing/solubilizing groups
attached. contained in Component Heterocyclic Rings (S--O
Bidentates, S--O Tridentates, S--O Tetradentates, and S--O
Hexadentates) S--O Valence Stabilizer #44: Macrocyclic ligands
containing a total of four to Four-, Five-, Six-, Seven-, Eight-,
Nine-, or ten five-membered heterocyclic rings containing
Ten-Membered Macrocyclics, sulfur or oxygen binding sites. Can
include Macrobicyclics, and Macropolycyclics other hydrocarbon/ring
systems bound to this (including Catapinands, Cryptands,
macrocyclic ligand, but they do not coordinate Cyclidenes, and
Sepulchrates) wherein all with the stabilized, high valence metal
ion. This Binding Sites are composed of Sulfur or ligand and/or
attached, uncoordinating Oxygen and are contained in Component 5-
hydrocarbon/rings may or may not have halogen Membered Heterocyclic
Rings (S--O or polarizing or water-insolubilizing groups
Tridentates, S--O Tetradentates or S--O attached. Hexadentates)
S--O Valence Stabilizer #45: Macrocyclic ligands containing at
least one Four-, Five-, Six-, Seven-, Eight-, Nine-, or
heterocyclic ring. These heterocyclic rings Ten-Membered
Macrocyclics, provide sulfur or oxygen binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, thiol,
mercapto, thiocarbonyl, hydroxy, carboxy, Cyclidenes, and
Sepulchrates) wherein all or carbonyl binding sites can also be
included in Binding Sites are composed of Sulfur or the macrocyclic
ligand, so long as the total Oxygen and are contained in a
Combination number of binding sites is four to ten. Can of
Heterocyclic Rings and Thiol, Mercapto, include other
hydrocarbon/ring systems bound Thiocarbonyl, Hydroxy, Carboxy, and
to this macrocyclic ligand, but they do not Carbonyl Groups (S--O
Tridentates, S--O coordinate with the stabilized, high valence
Tetradentates, or S--O Hexadentates) metal ion. This ligand and/or
attached, uncoordinating hydrocarbon/rings may or may not have
halogen or polarizing or water- insolubilizing groups attached.
S--O Valence Stabilizer #46: Sulfoxides (R--SO--R'), where R and R'
Sulfoxides (S--O Bidentates) represent H or any organic functional
group wherein the number of carbon atoms ranges from 0 to 35,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #47: Sulfones (R--SO.sub.2--R'), where R and R'
represent Sulfones (S--O Bidentates) H or any organic functional
group wherein the number of carbon atoms ranges from 0 to 35,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #48: Sulfur dioxide ligands (--SO.sub.2) bound directly
to Sulfur dioxide (SO.sub.2) ligands (S--O the high valence metal
ion. Bidentates) N--P Valence Stabilizer #1:
[R(--NR'R")(--PR"'R"")], [R(--NR'R").sub.x].sub.1-3P, [R Aminoaryl
Phosphines and Iminoaryl (--NR'R").sub.x].sub.1-3PX, or
[R(--PR'R").sub.x].sub.1-3N, where X = O Phosphines (N--P
Bidentates, N--P or S and R, R', R", R"', and R"" represents
Tridentates, and N--P Tetradentates) H, NH.sub.2 or any organic
functional group wherein the number of carbon atoms ranges from 0
to 35, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. N--P Valence Stabilizer
#2: Five membered heterocyclic ring(s) containing Heterocyclic
Rings containing One, Two, one, two, three, or four nitrogen atoms.
In Three, or Four Nitrogen Atoms at least one addition, ligand
contains additional phosphorus- additional Phosphorus Atom Binding
Site containing substituents that constitute P binding not in a
Ring (N--P Bidentates, N--P sites. Can include other ring systems
bound to Tridentates, N--P Tetradentates, or N--P the heterocyclic
ring or to the P-containing Hexadentates) substituent, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or P- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--P Valence
Stabilizer #3: Five membered heterocyclic ring(s) containing
Heterocyclic Rings containing One, Two, one, two, or three
phosphorus atoms. In or Three Phosphorus Atoms at least one
addition, ligand contains additional nitrogen- additional Nitrogen
Atom Binding Site not containing substituents (usually amines,
imines, in a Ring (N--P Bidentates, N--P Tridentates, or
hydrazides) that constitute N binding sites. N--P Tetradentates, or
N--P Hexadentates) Can include other ring systems bound to the
heterocyclic ring or to the N-containing substituent, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or N- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--P Valence
Stabilizer #4: Heterocyclic ring(s) containing one, two, three,
Heterocyclic Rings containing One, Two, or four nitrogen atoms. In
addition, ligand Three, or Four Nitrogen Atoms at least one
contains additional phosphorus-containing rings additional
Phosphorus Atom Binding Site that constitute P binding sites. Can
include in a Separate Ring (N--P Bidentates, N--P other ring
systems bound to the N- or P- Tridentates, N--P Tetradentates)
containing heterocyclic rings, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This ring(s) and/or additional P- containing ring(s)
and/or attached, uncoordinating rings may or may not have halogen
or polarizing or water- insolubilizing/solubilizing groups
attached. N--P Valence Stabilizer #5: Macrocyclic ligands
containing two, three, four, Two-, Three-, Four-, Five-, Six-,
Seven-, five, six, seven, eight, nine,
or ten binding sites Eight-, Nine-, and Ten-Membered composed of
nitrogen and phosphorus to Macrocyclics, Macrobicyclics, and
valence stabilize the central metal ion. Can Macropolycyclics
(including Catapinands, include other hydrocarbon or ring systems
Cryptands, Cyclidenes, and Sepulchrates) bound to this macrocyclic
ligand, but they do wherein all Binding Sites are composed of not
coordinate with the stabilized, high valence Nitrogen (usually
amine or imine groups) or metal ion. This ligand and/or attached,
Phosphorus and are not contained in uncoordinating
hydrocarbons/rings may or may Component Heterocyclic Rings (N--P
not have halogen or polarizing or water- Bidentates, N--P
Tridentates, N--P insolubilizing/solubilizing groups attached.
Tetradentates, and N--P Hexadentates) N--P Valence Stabilizer #6:
Macrocyclic ligands containing a total of four, Four-, Five-, Six-,
Seven-, Eight-, Nine-, or five, six, seven, eight, nine, or ten
heterocyclic Ten-Membered Macrocyclics, rings containing nitrogen
or phosphorus binding Macrobicyclics, and Macropolycyclics sites.
Can include other hydrocarbon/ring (including Catapinands,
Cryptands, systems bound to this macrocyclic ligand, but
Cyclidenes, and Sepulchrates) wherein all they do not coordinate
with the stabilized, high Binding Sites are composed of Nitrogen or
valence metal ion. This ligand and/or attached, Phosphorus and are
contained in uncoordinating hydrocarbon/rings may or may Component
Heterocyclic Rings (N--P not have halogen or polarizing or water-
Bidentates, N--P Tridentates, N--P insolubilizing groups attached.
Tetradentates, or N--P Hexadentates) N--P Valence Stabilizer #7:
Macrocyclic ligands containing at least one Four-, Five-, Six-,
Seven-, Eight-, Nine-, or heterocyclic ring. These heterocyclic
rings Ten-Membered Macrocyclics, provide nitrogen or phosphorus
binding sites to Macrobicyclics, and Macropolycyclics valence
stabilize the central metal ion. Other (including Catapinands,
Cryptands, amine, imine, or phosphine binding sites can Cyclidenes,
and Sepulchrates) wherein all also be included in the macrocyclic
ligand, so Binding Sites are composed of Nitrogen or long as the
total number of binding sites is four, Phosphorus and are contained
in a five, six, seven, eight, nine, or ten. Can include Combination
of Heterocyclic Rings and other hydrocarbon/ring systems bound to
this Amine, Imine, and Phosphine Groups (N--P macrocyclic ligand,
but they do not coordinate Bidentates, N--P Tridentates, N--P with
the stabilized, high valence metal ion. This Tetradentates, or N--P
Hexadentates) ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water-insolubilizing groups attached. S--P Valence Stabilizer #1:
[R(--SR').sub.x].sub.1-3P, [R(--SR').sub.x].sub.1-3PX, [R(--PR'R")
Thioaryl Phosphines (S--P Bidentates, S--P (--SR"')],
[R(--PR'R")(--S--S--R"')], [R(--PR'R") Tridentates, and S--P
Tetradentates) (--C(.dbd.S)R"'], [R(--PR'R").sub.x].sub.2S,
[R(--PR'R").sub.x].sub.2-3 R"'(--SR"').sub.y,
[R(--SR').sub.x].sub.2-3R"(--PR"'R"").sub.y, [R(--
PR'R").sub.x].sub.2S.sub.2, and
[R(--PR'R").sub.x].sub.2R"'(C(.dbd.S)).su- b.yR"", where X = O or
S, and R, R', R", R"', and R"" represent H, NH.sub.2, or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizi- ng groups attached, and x = 1-2 and y =
1-4. Ligand can also contain nonbinding N, O, S, or P atoms. S--P
Valence Stabilizer #2: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two sulfur atoms. In addition,
ligand contains Sulfur Atoms at least one additional additional
phosphorus-containing substituents Phosphorus Atom Binding Site not
in a that constitute P binding sites. Can include Ring (P--S
Bidentates, P--S Tridentates, P--S other ring systems bound to the
heterocyclic Tetradentates, or P--S Hexadentates) ring or to the
P-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This ring(s) and/or attached, uncoordinating rings
and/or P-containing substituent(s) may or may not have halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
S--P Valence Stabilizer #3: Heterocyclic ring(s) containing one,
two, or Heterocyclic Rings containing One, Two, three phosphorus
atoms. In addition, ligand or Three Phosphorus Atoms at least one
contains additional sulfur-containing additional Sulfur Atom
Binding Site not in substituents (usually thiol, mercapto, or a
Ring (S--P Bidentates, S--P Tridentates, S--P thiocarbonyl groups)
that constitute S binding P Tetradentates, or S--P Hexadentates)
sites. Can include other ring systems bound to the heterocyclic
ring or to the S-containing substituent, but they do not coordinate
with the stabilized, high valence metal ion. Ring(s) can also
contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S--P Valence
Stabilizer #4: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two sulfur atoms. In addition,
ligand contains Sulfur Atoms at least one additional additional
phosphorus-containing rings that Phosphorus Atom Binding Site in a
constitute P binding sites. Can include other Separate Ring (S--P
Bidentates, S--P ring systems bound to the S- or P-containing
Tridentates, S--P Tetradentates) heterocyclic rings, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or additional
P-containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S--P Valence
Stabilizer #5: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight,
nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed
of sulfur and phosphorus to valence Macrocyclics, Macrobicyclics,
and stabilize the central metal ion. Can include other
Macropolycyclics (including Catapinands, hydrocarbon or ring
systems bound to this Cryptands, Cyclidenes, and Sepulchrates)
macrocyclic ligand, but they do not coordinate wherein all Binding
Sites are composed of with the stabilized, high valence metal ion.
This Sulfur (usually thiol, mercapto, or ligand and/or attached,
uncoordinating thiocarbonyl groups) or Phosphorus and are
hydrocarbons/rings may or may not have not contained in Component
Heterocyclic halogen or polarizing or water- Rings (S--P
Bidentates, S--P Tridentates, S--P insolubilizing/solubilizing
groups attached. Tetradentates, and S--P Hexadentates) S--P Valence
Stabilizer #6: Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, Nine-, or five, six, seven,
eight, nine, or ten heterocyclic Ten-Membered Macrocyclics, rings
containing sulfur or phosphorus binding Macrobicyclics, and
Macropolycyclics sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands, systems bound to this
macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all
they do not coordinate with the stabilized, high Binding Sites are
composed of Sulfur or valence metal ion. This ligand and/or
attached, Phosphorus and are contained in uncoordinating
hydrocarbon/rings may or may Component Heterocyclic Rings (S--P not
have halogen or polarizing or water- Bidentates, S--P Tridentates,
S--P insolubilizing groups attached. Tetradentates, or S--P
Hexadentates) S--P Valence Stabilizer #7: Macrocyclic ligands
containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-,
or heterocyclic ring. These heterocyclic rings Ten-Membered
Macrocyclics, provide sulfur or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, thiol,
mercapto, or thiocarbonyl, or phosphine Cyclidenes, and
Sepulchrates) wherein all binding sites can also be included in the
Binding Sites are composed of Sulfur or macrocyclic ligand, so long
as the total number Phosphorus and are contained in a of binding
sites is four, five, six, seven, eight, Combination of Heterocyclic
Rings and nine, or ten. Can include other Thiol, Mercapto,
Thiocarbonyl or hydrocarbon/ring systems bound to this Phosphine
Groups (S--P Bidentates, S--P macrocyclic ligand, but they do not
coordinate Tridentates, S--P Tetradentates, or S--P with the
stabilized, high valence metal ion. This Hexadentates) ligand
and/or attached, uncoordinating hydrocarbon/rings may or may not
have halogen or polarizing or water-insolubilizing groups attached.
P--O Valence Stabilizer #1: [R(--OR').sub.x].sub.1-3P,
[R(--OR').sub.x].sub.1-3PX, [R(--PR'R"(-- Hydroxyaryl Phosphines
(P--O Bidentates, OR"')], [R(--PR'R")(--C(.dbd.O)R"'], [R(-- P--O
Tridentates, and P--O Tetradentates) PR'R").sub.x].sub.2O,
[R(--PR'R").sub.x].sub.2-3R"'(--OR"").sub.y, [R(--
OR').sub.x].sub.2-3R"(--PR"'R"").sub.y, and [R(--
PR'R").sub.x].sub.2R"'(C(.dbd.O)).sub.yR"", where X = O or S, and
R, R', R",and R"', and R"" represent H, NH.sub.2, or any organic
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached, and x = 1-2 and
y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms.
P--O Valence Stabilizer #2: Heterocyclic ring(s) containing one or
two Heterocyclic Rings containing One or Two oxygen atoms. In
addition, ligand contains Oxygen Atoms at least one additional
additional phosphorus-containing substituents Phosphorus Atom
Binding Site not in a that constitute P binding sites. Can include
Ring (P--O Bidentates, P--O Tridentates, P--O other ring systems
bound to the heterocyclic Tetradentates, or P--O Hexadentates) ring
or to the P-containing substituent, but they do not coordinate with
the stabilized, high valence metal ion. Ring(s) can also contain O,
S, or P atoms. This ring(s) and/or attached, uncoordinating rings
and/or P-containing substituent(s) may or may not have halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
P--O Valence Stabilizer #3: Heterocyclic ring(s) containing one,
two, or Heterocyclic Rings containing One, Two, three phosphorus
atoms. In addition, ligand or Three Phosphorus Atoms at least one
contains additional oxygen-containing additional Oxygen Atom
Binding Site not substituents (usually hydroxy, carboxy, or in a
Ring (P--O Bidentates, P--O Tridentates, carbonyl groups) that
constitute O binding sites. P--O Tetradentates, or P--O
Hexadentates) Can include other ring systems bound to the
heterocyclic ring or to the O-containing substituent, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or O- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P--O Valence
Stabilizer #4: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two oxygen atoms. In addition,
ligand contains Oxygen Atoms at least one additional additional
phosphorus-containing rings that Phosphorus Atom Binding Site in a
constitute P binding sites. Can include other Separate Ring (P--O
Bidentates, P--O ring systems bound to the O- or P-containing
Tridentates, P--O Tetradentates) heterocyclic rings, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or additional
P-containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P--O Valence
Stabilizer #5: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight,
nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed
of oxygen and phosphorus to valence Macrocyclics, Macrobicyclics,
and stabilize the central metal ion. Can include other
Macropolycyclics (including Catapinands, hydrocarbon or ring
systems bound to this Cryptands, Cyclidenes, and Sepulchrates)
macrocyclic ligand, but they do not coordinate wherein all Binding
Sites are composed of with the stabilized, high valence metal ion.
This Oxygen (usually hydroxy, carboxy, or ligand and/or attached,
uncoordinating carbonyl groups) or Phosphorus and are not
hydrocarbons/rings may or may not have contained in Component
Heterocyclic halogen or polarizing or water- Rings (P--O
Bidentates, P--O Tridentates, P--O insolubilizing/solubilizing
groups attached. Tetradentates, and P--O Hexadentates) P--O Valence
Stabilizer #6: Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, Nine-, or five, six, seven,
eight, nine, or ten heterocyclic Ten-Membered Macrocyclics, rings
containing oxygen or phosphorus binding Macrobicyclics, and
Macropolycyclics sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands, systems bound to this
macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all
they do not coordinate with the stabilized, high Binding Sites are
composed of Oxygen or valence metal ion. This ligand and/or
attached, Phosphorus and are contained in uncoordinating
hydrocarbon/rings may or may Component Heterocyclic Rings (P--O not
have halogen or polarizing or water- Bidentates, P--O Tridentates,
P--O insolubilizing groups attached. Tetradentates, or P--O
Hexadentates) P--O Valence Stabilizer #7: Macrocyclic ligands
containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-,
or heterocyclic ring. These heterocyclic rings Ten-Membered
Macrocyclics, provide oxygen or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, hydroxy,
carboxy, carbonyl, or phosphine Cyclidenes, and Sepulchrates)
wherein all binding sites can also be included in the Binding Sites
are composed of Oxygen or macrocyclic ligand, so long as the total
number Phosphorus and are contained in a of binding sites is four,
five, six, seven, eight, Combination of Heterocyclic Rings and
nine, or ten. Can include other Hydroxy, Carboxy, Carbonyl or
Phosphine hydrocarbon/ring systems bound to this Groups (P--O
Bidentates, P--O Tridentates, macrocyclic ligand, but they do not
coordinate P--O Tetradentates, or P--O Hexadentates) with the
stabilized, high valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water-insolubilizing groups attached. As Valence
Stabilizer #1: AsH.sub.3, AsH.sub.2R, AsHR.sub.2, where R
represents H or Monoarsines (As Monodentates) wherein at any
organic functional group wherein the least one Arsenic Atom is a
Binding Site number of carbon atoms ranges from 0 to 25, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, As, O, S,
or Se atoms. As Valence Stabilizer #2: R'--As--R--As--R", where R,
R', and R" represent Diarsines (an As--As Bidentate) wherein at H
or any organic functional group wherein the least one Arsenic Atom
is a Binding Site number of carbon atoms ranges from 0 to 25,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. As Valence
Stabilizer #3: R--As--R'--As--R"--As--R"', where R, R', R", and
Triarsines (either As--As Bidentates or As-- R"' represent H or
any
organic functional group As Tridentates) wherein at least one
wherein the number of carbon atoms ranges Arsenic Atom is a Binding
Site from 0 to 25, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. As Valence
Stabilizer #4: R--As--R'--As--R"--As--R"'--As--R"", where R, R',
Tetraarsines (As--As Bidentates, As--As R", R"', and R"" represent
H or any organic Tridentates, or As--As Tetradentates) functional
group wherein the number of carbon wherein at least one Arsenic
Atom is a atoms ranges from 0 to 25, optionally having Binding Site
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, P, As, O, S, or Se
atoms. As Valence Stabilizer #5:
R--As--R'--As--R"--As--R"'--As--R""--As--R""', Pentaarsines (As--As
Bidentates, As--As where R, R', R", R"', R"", and R""' represent H
Tridentates, or As--As Tetradentates) or any organic functional
group wherein the wherein at least one Arsenic Atom is a number of
carbon atoms ranges from 0 to 25, Binding Site optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, P, As, O, S, or Se
atoms. As Valence Stabilizer #6:
R--As--R'--As--R"--As--R"'--As--R""--As--R""'--As-- - Hexaarsines
(As--As Bidentates, As--As R""", where R, R', R", R"', R"", R""',
and Tridentates, As--As Tetradentates, or As--As R""" represent H
or any organic functional Hexadentates) wherein at least one
Arsenic group wherein the number of carbon atoms Atom is a Binding
Site ranges from 0 to 25, optionally having halogen or polarizing
or water- insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, P, As, O, S, or Se atoms. As Valence
Stabilizer #7: Five membered heterocyclic ring containing just
Five-Membered Heterocyclic Rings one arsenic binding site. Can
include other ring containing One Arsenic Atom wherein the systems
bound to this heterocyclic ring, but they Arsenic Atom is the
Binding Site (As do not coordinate with the stabilized, high
Monodentates) valence metal ion. Ring can also contain O, S, N, P,
or Se atoms. This 5-membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. As Valence Stabilizer
#8: Six membered heterocyclic ring containing just Six-Membered
Heterocyclic Rings one arsenic binding site. Can include other ring
containing One Arsenic Atom wherein the systems bound to this
heterocyclic ring, but they Arsenic Atom is the Binding Site (As do
not coordinate with the stabilized, high Monodentates) valence
metal ion. Ring can also contain O, S, N, P, or Se atoms. This
6-membered ring and/or attached, uncoordinating rings may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. As Valence Stabilizer
#9: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one arsenic atom. In addition, ligand contains
containing One Arsenic Atom and having at additional
arsenic-containing substituents least one additional Arsenic Atom
Binding (usually arsines) that constitute As binding sites. Site
not in a Ring (As Monodentates, As--As Can include other ring
systems bound to the Bidentates, As--As Tridentates, As--As
heterocyclic ring or to the As-containing Tetradentates, or As--As
Hexadentates) substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, N,
S, P or Se atoms. This 5- membered ring(s) and/or attached,
uncoordinating rings and/or As-containing substituent(s) may or may
not have halogen or polarizing or water-insolubilizing/solubilizing
groups attached. As Valence Stabilizer #10: Six membered
heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one
arsenic atom. In addition, ligand contains containing One Arsenic
Atom and having at additional arsenic-containing substituents least
one additional Arsenic Atom Binding (usually arsines) that
constitute As binding sites. Site not in a Ring (As Monodentates,
As--As Can include other ring systems bound to the Bidentates,
As--As Tridentates, As--As heterocyclic ring or to the
As-containing Tetradentates, or As--As Hexadentates) substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, N, S, P or Se atoms. This 6-
membered ring(s) and/or attached, uncoordinating rings and/or
As-containing substituent(s) may or may not have halogen or
polarizing or water-insolubilizing/solubilizing groups attached. As
Valence Stabilizer #11: Five membered heterocyclic ring(s)
containing Five-Membered Heterocyclic Rings one arsenic atom. In
addition, ligand contains containing One Arsenic Atom and having at
additional arsenic-containing rings that least one additional
Arsenic Atom Binding constitute As binding sites. Can include other
Site in a separate Ring (As Monodentates, ring systems bound to the
As-containing As--As Bidentates, As--As Tridentates, As--
heterocyclic rings, but they do not coordinate As Tetradentates, or
As--As Hexadentates) with the stabilized, high valence metal ion.
Ring(s) can also contain O, N, S, P, or Se atoms. This 5-membered
ring(s) and/or additional As-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. As Valence
Stabilizer #12: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one arsenic atom. In addition,
ligand contains containing One Arsenic Atom and having at
additional arsenic-containing rings that least one additional
Arsenic Atom Binding constitute As binding sites. Can include other
Site in a separate Ring (As Monodentates, ring systems bound to the
As-containing As--As Bidentates, As--As Tridentates, As--
heterocyclic rings, but they do not coordinate As Tetradentates, or
As--As Hexadentates) with the stabilized, high valence metal ion.
Ring(s) can also contain O, N, S, P, or Se atoms. This 6-membered
ring(s) and/or additional As-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. As Valence
Stabilizer #13: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, and Six-Membered or six arsenic binding sites
to valence stabilize Macrocyclics, Macrobicyclics, and the central
metal ion. Can include other Macropolycyclics (including
Catapinands, hydrocarbon or ring systems bound to this Cryptands,
Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not
coordinate wherein all Binding Sites are composed of with the
stabilized, high valence metal ion. This Arsenic and are not
contained in ligand and/or attached, uncoordinating Component
Heterocyclic Rings (As--As hydrocarbons/rings may or may not have
Bidentates, As--As Tridentates, As--As halogen or polarizing or
water- Tetradentates, and As--As Hexadentates)
insolubilizing/solubilizing groups attached. As Valence Stabilizer
#14: Macrocyclic ligands containing a total of four or Four-, or
Six-Membered Macrocyclics, six five-membered heterocyclic rings
containing Macrobicyclics, and Macropolycyclics arsenic binding
sites. Can include other (including Catapinands, Cryptands,
hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Arsenic and with the
stabilized, high valence metal ion. This are contained in Component
5-Membered ligand and/or attached, uncoordinating Heterocyclic
Rings (As--As Tridentates, As-- hydrocarbon/rings may or may not
have halogen As Tetradentates, or As--As Hexadentates) or
polarizing or water-insolubilizing groups attached. As Valence
Stabilizer #15: Macrocyclic ligands containing at least one 5-
Four-, or Six-Membered Macrocyclics, membered heterocyclic ring.
These Macrobicyclics, and Macropolycyclics heterocyclic rings
provide arsenic binding sites (including Catapinands, Cryptands, to
valence stabilize the central metal ion. Other Cyclidenes, and
Sepulchrates) wherein all arsine binding sites can also be included
in the Binding Sites are composed of Arsenic and macrocyclic
ligand, so long as the total number are contained in a Combination
of 5- of binding sites is four or eight. Can include Membered
Heterocyclic Rings and Arsine other hydrocarbon/ring systems bound
to this Groups (As--As Tridentates, As--As macrocyclic ligand, but
they do not coordinate Tetradentates, or As--As Hexadentates) with
the stabilized, high valence metal ion. This ligand and/or
attached, uncoordinating hydrocarbon/rings may or may not have
halogen or polarizing or water-insolubilizing groups attached. As
Valence Stabilizer #16: Macrocyclic ligands containing a total of
four or Four-, or Six-Membered Macrocyclics, six six-membered
heterocyclic rings containing Macrobicyclics, and Macropolycyclics
arsenic binding sites. Can include other (including Catapinands,
Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Arsenic and with the
stabilized, high valence metal ion. This are contained in Component
6-Membered ligand and/or attached, uncoordinating Heterocyclic
Rings (As--As Tridentates, As-- hydrocarbon/rings may or may not
have halogen As Tetradentates, or As--As Hexadentates) or
polarizing or water-insolubilizing groups attached. As Valence
Stabilizer #17: Macrocyclic ligands containing at least one 6-
Four-, or Six-Membered Macrocyclics, membered heterocyclic ring.
These Macrobicyclics, and Macropolycyclics heterocyclic rings
provide arsenic binding sites (including Catapinands, Cryptands, to
valence stabilize the central metal ion. Other Cyclidenes, and
Sepulchrates) wherein all arsine binding sites can also be included
in the Binding Sites are composed of Arsenic and macrocyclic
ligand, so long as the total number are contained in a Combination
of 6- of binding sites is four or six. Can include other Membered
Heterocyclic Rings and Arsine hydrocarbon/ring systems bound to
this Groups (As--As Tridentates, As--As macrocyclic ligand, but
they do not coordinate Tetradentates, or As--As Hexadentates) with
the stabilized, high valence metal ion. This ligand and/or
attached, uncoordinating hydrocarbon/rings may or may not have
halogen or polarizing or water-insolubilizing groups attached. Se
Valence Stabilizer #1: SeH.sub.2, SeHR, SeR.sub.2, where R
represents H or any Monoselenoethers (Se Monodentates) organic
functional group wherein the number of wherein at least one
Selenium Atom is a carbon atoms ranges from 0 to 25, optionally
Binding Site having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer
#2: R--Se--R'--Se--R", where R, R', and R" represents
Diselenoethers (Se--Se Bidentates) wherein H or any organic
functional group wherein the at least one Selenium Atom is a
Binding number of carbon atoms ranges from 0 to 25, Site optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, O, S, or
Se atoms. Se Valence Stabilizer #3: R--Se--R'--Se--R"--Se--R"',
where R, R', R", and Triselenoethers (Se--Se Bidentates or Se--Se
R"' represents H or any organic functional Tridentates) wherein at
least one Selenium group wherein the number of carbon atoms Atom is
a Binding Site ranges from 0 to 25, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. Se
Valence Stabilizer #4: R--Se--R'--Se--R"--Se--R"'--Se--R"", where
R,R', Tetraselenoethers (Se--Se Bidentates, Se--Se R", R"', and R""
represents H or any organic Tridentates, or Se--Se Tetradentates)
functional group wherein the number of carbon wherein at least one
Selenium Atom is a atoms ranges from 0 to 25, optionally having
Binding Site halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer
#5: Five membered heterocyclic ring containing one Five-Membered
Heterocyclic Rings or two selenium atoms, both of which may
containing One or Two Selenium Atoms function as binding sites. Can
include other wherein at least one Selenium Atom is a ring systems
bound to this heterocyclic ring, but Binding Site (Se Monodentates
or Se--Se they do not coordinate with the stabilized, high
Bidentates) valence metal ion. Ring can also contain O, N, P, As,
or S atoms. This 5-membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#6: Six membered heterocyclic ring containing one Six-Membered
Heterocyclic Rings or two selenium atoms, both of which may
containing One or Two Selenium Atoms function as binding sites. Can
include other wherein at least one Selenium Atom is a ring systems
bound to this heterocyclic ring, but Binding Site (Se Monodentates
or Se--Se they do not coordinate with the stabilized, high
Bidentates) valence metal ion. Ring can also contain O, N, P, As,
or S atoms. This 5-membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#7: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one selenium atom. In addition, ligand contains
containing One Selenium Atom and having additional
selenium-containing substituents at least one additional Selenium
Atom (usually selenols or selenoethers) that constitute Binding
Site not in a Ring (Se Se binding sites. Can include other ring
Monodentates, Se--Se Bidentates, Se--Se systems bound to the
heterocyclic ring or to the Tridentates, Se--Se Tetradentates, or
Se--Se Se-containing substituent, but they do not Hexadentates)
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, N, P, As or S atoms. This 5-membered ring(s) and/or
attached, uncoordinating rings and/or Se- containing substituent(s)
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#8: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one selenium atom. In addition, ligand contains
containing One Selenium Atom and having additional
selenium-containing substituents at least one additional Selenium
Atom (usually selenols or selenoethers) that constitute Binding
Site not in a Ring (Se Se binding sites. Can include other ring
Monodentates, Se--Se Bidentates, Se--Se systems bound to the
heterocyclic ring or to the Tridentates, Se--Se Tetradentates, or
Se--Se Se-containing substituent, but they do not Hexadentates)
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, N, P, As or S atoms. This 6-membered ring(s) and/or
attached, uncoordinating rings and/or Se- containing substituent(s)
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#9: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one selenium atom. In addition, ligand contains
containing One Selenium Atom and having additional
selenium-containing rings that at least one additional Selenium
Atom constitute Se binding sites. Can include other Binding Site in
a separate Ring (Se ring systems bound to the Se-containing
Monodentates, Se--Se Bidentates, Se--Se heterocyclic
rings, but they do not coordinate Tridentates, Se--Se
Tetradentates, or Se--Se with the stabilized, high valence metal
ion. Hexadentates) Ring(s) can also contain O, N, P, As, or S
atoms. This 5-membered ring(s) and/or additional Se-containing
ring(s) and/or attached, uncoordinating rings may or may not have
halogen or polarizing or water- insolubilizing/solubilizi- ng
groups attached. Se Valence Stabilizer #10: Six membered
heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one
selenium atom. In addition, ligand contains containing One Selenium
Atom and having additional selenium-containing rings that at least
one additional Selenium Atom constitute Se binding sites. Can
include other Binding Site in a separate Ring (Se ring systems
bound to the Se-containing Monodentates, Se--Se Bidentates, Se--Se
heterocyclic rings, but they do not coordinate Tridentates, Se--Se
Tetradentates, or Se--Se with the stabilized, high valence metal
ion. Hexadentates) Ring(s) can also contain O, N, P, As, or S
atoms. This 6-membered ring(s) and/or additional Se-containing
ring(s) and/or attached, uncoordinating rings may or may not have
halogen or polarizing or water- insolubilizing/solubilizi- ng
groups attached. Se Valence Stabilizer #11: Macrocyclic ligands
containing two, three, four, Two-, Three-, Four-, or Six-Membered
or six selenium binding sites to valence stabilize Macrocyclics,
Macrobicyclics, and the central metal ion. Can include other
Macropolycyclics (including Catapinands, hydrocarbon or ring
systems bound to this Cryptands, Cyclidenes, and Sepulchrates)
macrocyclic ligand, but they do not coordinate wherein all Binding
Sites are composed of with the stabilized, high valence metal ion.
This Selenium (usually selenol or selenoether ligand and/or
attached, uncoordinating groups) and are not contained in
hydrocarbons/rings may or may not have Component Heterocyclic Rings
(Se--Se halogen or polarizing or water- Bidentates, Se--Se
Tridentates, Se--Se insolubilizing/solubilizing groups attached.
Tetradentates, or Se--Se Hexadentates) Se Valence Stabilizer #12:
Macrocyclic ligands containing a total of four or Four-, or
Six-Membered Macrocyclics, six five-membered heterocyclic rings
containing Macrobicyclics, and Macropolycyclics selenium binding
sites. Can include other (including Catapinands, Cryptands,
hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Selenium with the
stabilized, high valence metal ion. This and are contained in
Component 5- ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (Se--Se hydrocarbon/rings may or may not have
halogen Tridentates, Se--Se Tetradentates or Se--Se or polarizing
or water-insolubilizing groups Hexadentates) attached. Se Valence
Stabilizer #13: Macrocyclic ligands containing at least one 5-
Four-, or Six-Membered Macrocyclics, membered heterocyclic ring.
These Macrobicyclics, and Macropolycyclics heterocyclic rings
provide selenium binding (including Catapinands, Cryptands, sites
to valence stabilize the central metal ion. Cyclidenes, and
Sepulchrates) wherein all Other selenol or selenoether binding
sites can Binding Sites are composed of Selenium also be included
in the macrocyclic ligand, so and are contained in a Combination of
5- long as the total number of binding sites is four Membered
Heterocyclic Rings and Selenol or six. Can include other
hydrocarbon/ring or Selenoether Groups (Se--Se Tridentates, systems
bound to this macrocyclic ligand, but Se--Se Tetradentates, or
Se--Se they do not coordinate with the stabilized, high
Hexadentates) valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. Se Valence
Stabilizer #14: Macrocyclic ligands containing a total of four or
Four-, or Six-Membered Macrocyclics, six six-membered heterocyclic
rings containing Macrobicyclics, and Macropolycyclics selenium
binding sites. Can include other (including Catapinands, Cryptands,
hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Selenium with the
stabilized, high valence metal ion. This and are contained in
Component 6- ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (Se--Se hydrocarbon/rings may or may not have
halogen Tridentates, Se--Se Tetradentates, or Se--Se or polarizing
or water-insolubilizing groups Hexadentates) attached. Se Valence
Stabilizer #15: Macrocyclic ligands containing at least one 6-
Four-, or Six-Membered Macrocyclics, membered heterocyclic ring.
These Macrobicyclics, and Macropolycyclics heterocyclic rings
provide selenium binding (including Catapinands, Cryptands, sites
to valence stabilize the central metal ion. Cyclidenes, and
Sepulchrates) wherein all Other selenol or selenoether binding
sites can Binding Sites are composed of Selenium also be included
in the macrocyclic ligand, so and are contained in a Combination of
6- long as the total number of binding sites is four Membered
Heterocyclic Rings and Selenol or six. Can include other
hydrocarbon/ring or Selenoether Groups (Se--Se Tridentates, systems
bound to this macrocylic ligand, but Se--Se Tetradentates, or
Se--Se they do not coordinate with the stabilized, high
Hexadentates) valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. Se Valence
Stabilizer #16: R--C(.dbd.Se)--CR'R'--C(.dbd.Se)--R"'where R, R',
R", 1,3-Diselenoketones (Diseleno-beta- and R"' represent H,
NH.sub.2, or any organic ketonates), 1,3,5-Triselenoketones,
Bis(1,3- functional group wherein the number of carbon
Diselenoketones), and Poly( 1,3- atoms ranges from 0 to 40,
optionally having Diselenoketones) (S--S Bidentates, S--S halogen
or polarizing or water- Tridentates, S--S Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #17:
RR'--C.dbd.C(--Se)(--Se), where R and R'represent
1,1-Diselenolates, Bis(1,1-diselenolates), H, NH.sub.2 or any
organic functional group wherein and Poly(1,1-diselenolates)
(Se--Se the number of carbon atoms ranges from 0 to Bidentates and
Se--Se Tetradentates) 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer
#18: RR'N.sup.+.dbd.C(SeH)(SeH), where R and R' Diselenocarbamates,
represent H, OH, SH, OR"(R".dbd.C.sub.1--C.sub.30 alkyl or
Bis(diselenocarbamates), and aryl), SR" (R".dbd.C.sub.1--C.sub.30
alkyl or aryl), NH.sub.2 or Poly(diselenocarbamates) (including N-
any organic functional group wherein the hydroxydiselenocarbamates
and N-- number of carbon atoms ranges from 0 to 40,
mercaptodiselenocarbamates) (Se--Se optionally having halogen or
polarizing or Bidentates, Se--Se Tridentates, and Se--Se
water-insolubilizing/solubilizing groups Tetradentates) attached.
Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence
Stabilizer #19: (O.dbd.)P(--Se--R)(--Se-- -R')(--Se--R") or
(Se.dbd.)P(--Se-- Triselenophosphoric Acids R)(--Se--R')(--O--R"),
where R, R', and R" (Phosphorotriselenoic Acids), represent H,
NH.sub.2 or any organic functional Bis(triselenophosphoric acids),
group wherein the number of carbon atoms Poly(triselenophosphoric
acids), and ranges from 0 to 40, optionally having halogen
derivatives thereof (Se--Se Bidentates, Se--Se or polarizing or
water- Tridentates, Se--Se Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #20:
(O.dbd.)P(--Se--R)(--Se--R')(--O--R") or (Se.dbd.)P(--Se--
Diselenophosphoric Acids R)(--O--R')(--O--R"), where R, R', and R"
(Phosphorodiselenoic Acids), represent H, NH.sub.2 or any organic
functional Bis(diselenophosphoric acids), group wherein the number
of carbon atoms Poly(diselenophosphoric acids), and ranges from 0
to 40, optionally having halogen derivatives thereof (Se--Se
Bidentates, Se--Se or polarizing or water- Tridentates, Se--Se
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. Se Valence
Stabilizer #21: (Se.dbd.)P(--Se--R)(--Se--R')(- --Se--R"), where R,
R', Tetraselenophosphoric Acids and R" represent H, NH.sub.2 or any
organic (Phosphorotetraselenoic Acids), functional group wherein
the number of carbon Bis(tetraselenophosphoric acids), atoms ranges
from 0 to 40, optionally having Poly(tetraselenophosphoric acids),
and halogen or polarizing or water- derivatives thereof (Se--Se
Bidentates, Se--Se insolubilizing/solubilizing groups attached.
Tridentates, Se--Se Tetradentates) Ligand can also contain
nonbinding N, O, S, or P atoms. Se Valence Stabilizer #22:
R--Se--C(.dbd.Se)--O--R' or R--Se--C(.dbd.O)--Se--R' for
Diselenocarbonates, Triselenocarbonates, diselenocarbonates, and
R--Se--C(.dbd.Se)--Se--R' for Bis(diselenocarbonates), and
triselenocarbonates, where R, and R' represent
Bis(triselenocarbonates), (Se--Se Bidentates H, NH.sub.2 or any
organic functional group wherein and Se--Se Tetradentates) the
number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
Se Valence Stabilizer #23: Selenocyanates bound directly to the
high Selenocyanates (Se Monodentates) valence metal ion. Se Valence
Stabilizer #24: Selenolates (HSe--R, HSe--R--SeH, etc.), where R
Selenolates (Se Monodentates) and R'represent H or any organic
functional group wherein the number of carbon atoms ranges from 0
to 35, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Miscellaneous Valence
Stabilizer #1: Dialkenes or bicyclic or tricyclic hydrocarbons
Diene or bicyclic or tricyclic hydrocarbon bound directly to the
high valence metal ion. ligands Miscellaneous Valence Stabilizer
#2: Cyanide and cyanate and related ligands bound Cyanide and
related ligands directly to the high valence metal ion.
Miscellaneous Valence Stabilizer #3: Carbonyl (--CO) ligands bound
directly to the Carbonyl ligands high valence metal ion.
Miscellaneous Valence Stabilizer #4: Halogen (X) atoms bound
directly to the high Halogen ligands valence metal ion.
[0358] N Valence Stabilizer #1a: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates or N--N Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: pentaazacyclodecane
([10]aneN.sub.5); pentaazacycloundecane ([11]aneN.sub.5);
pentaazacyclododecane ([12]aneN.sub.5); pentaazacyclotridecane
([13]aneN.sub.5); pentazaacyclotetradecane ([14]aneN.sub.5);
pentaazacyclopentadecane ([15]aneN.sub.5); pentaazacyclodecatriene
([10]trieneN.sub.5); pentaazacycloundecatriene ([11]trieneN.sub.5);
pentaazacyclododecatriene ([12 trieneN.sub.5);
pentaazacyclotridecatriene ([13]trieneN.sub.5);
pentazaacyclotetradecatri- ene ([14]trieneN.sub.5); and
pentaazacyclopentadecatriene ([15]trieneN.sub.5).
[0359] N Valence Stabilizer #1b: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
heptaazacyclotetradecane ([14]aneN.sub.7); heptaazacyclopentadecane
([15]aneN.sub.7); heptaazacyclohexadecanc ([16]aneN.sub.7);
heptaazacycloheptadecane ([17]aneN.sub.7); heptaazacyclooctadecane
([18]aneN.sub.7); heptaazacyclononadecane ([19]aneN.sub.7);
heptaazacycloeicosane ([20]aneN.sub.7); heptaazacycloheneicosane
([21] aneN.sub.7); heptaazacyclotetradecatriene
([14]trieneN.sub.7); heptaazacyclopentadecatriene
([15]trieneN.sub.7); heptaazacyclohexadecatriene
([16]trieneN.sub.7); heptaazacycloheptadecatr- iene
([17]trieneN.sub.7); heptaazacyclooctadecatriene
([18]trieneN.sub.7); heptaazacyclononadecatriene
([19]trieneN.sub.7); heptaazacycloeicosatrien- e
([20]trieneN.sub.7); and heptaazacycloheneicosatriene
([21]trieneN.sub.7).
[0360] N Valence Stabilizer #1c: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen (usually amine or imine
groups) and are not contained in component heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
include, but are not limited to: nonaazacyclooctadecane
([18]aneN.sub.9); nonaazacyclononadecane ([19]aneN.sub.9);
nonaazacycloeicosane ([20]aneN.sub.9); nonaazacycloheneicosane
([21]aneN.sub.9); nonaazacyclodocosane ([22]aneN.sub.9);
nonaazacyclotricosane ([23]aneN.sub.9); nonaazacyclotetracosane
([24]aneN.sub.9); nonaazacyclopentacosane ([25]aneN.sub.9);
nonaazacyclohexacosane ([26]aneN.sub.9); nonaazacycloheptacosane
([27]aneN.sub.9); nonaazacyclooctadecatetradiene
([18]tetradieneN.sub.9); nonaazacyclononadecatetradiene
([19]tetradieneN.sub.9); nonaazacycloeicosatetradiene
([20]tetradieneN.sub.9); nonaazacycloheneicosatetradiene
([21]tetradieneN.sub.9); nonaazacyclodocosatetradiene
([22]tetradieneN.sub.9); nonaazacyclotricosatetradiene
([23]tetradieneN.sub.9); nonaazacyclotetracosatetradiene
([24]tetradieneN.sub.9); nonaazacyclopentacosatetradiene
([25]tetradieneN.sub.9); nonaazacyclohexacosatetradiene
([26]tetradieneN.sub.9); and nonaazacycloheptacosatetradiene
([27]tetradieneN.sub.9).
[0361] N Valence Stabilizer #2a: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of nitrogen and are contained in
component 5-membered heterocyclic rings (N--N Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
pentaphyrins (pentapyrroles); sapphyrins; smaragdyrins;
pentaoxazoles; pentaisooxazoles; pentathiazoles; pentaisothiazoles;
pentaazaphospholes; pentaimidazoles; pentapyrazoles;
pentaoxadiazoles; pentathiadiazoles; pentadiazaphospholes;
pentatriazoles; pentaoxatriazoles; and pentathiatriazoles.
[0362] N Valence Stabilizer #2b: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of nitrogen and are contained in
component 5-membered heterocyclic rings (N--N Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
heptaphyrins (heptapyrroles); heptaoxazoles; heptaisooxazoles;
heptathiazoles; heptaisothiazoles; heptaazaphospholes;
heptaimidazoles; heptapyrazoles; heptaoxadiazoles;
heptathiadiazoles; heptadiazaphospholes; heptatriazoles;
heptaoxatriazoles; and heptathiatriazoles.
[0363] N Valence Stabilizer #3a: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tridentates or N--N Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
superphthalocyanine; supernaphthalocyanine; diazapentaphyrins;
tetraazapentaphyrins; pentaazapentaphyrins; diazapentapyrazoles;
tetraazapentapyrazoles; pentaazapentapyrazoles;
diazapentaimidazoles; tetraazapentaimidazoles; and
pentaazapentaimidazoles.
[0364] N Valence Stabilizer #3b: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazabeptaphyrins; tetraazaheptaphyrins;
hexaazaheptaphyrins; diazaheptapyrazoles; tetraazaheptapyrazoles;
hexaazaheptapyrazoles; diazaheptaimidazoles;
tetraazaheptaimidazoles; and hexaazaheptaimidazoles.
[0365] N Valence Stabilizer #3c: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
nine binding sites are composed of nitrogen and are contained in a
combination of 5-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,-but are not
limited to: diazanonaphyrins; tetraazanonaphyrins;
hexaazanonaphyrins; diazanonapyrazoles; tetraazanonapyrazoles;
hexaazanonapyrazoles; diazanonaimidazoles; tetraazanonaimidazoles;
and hexaazanonaimidazoles.
[0366] N Valence Stabilizer #4a: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of nitrogen and are contained in
component 6-membered heterocyclic rings (N--N Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
cyclopentapyridines; cyclopentaoxazines; cyclopentathiazines;
cyclopentaphosphorins; cyclopentaquinolines; cyclopentapyrazines;
cyclopentapyridazines; cyclopentapyrimidines;
cyclopentaoxadiazines; cyclopentathiadiazines;
cyclopentadiazaphosphorins cyclopentaquinoxalines;
cyclopentatriazines; cyclopentathiatriazines; and
cyclopentaoxatriazines.
[0367] N Valence Stabilizer #4b: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of nitrogen and are contained in
component 6-membered heterocyclic rings (N--N Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
cycloheptapyridines; cycloheptaoxazines; cycloheptathiazines;
cycloheptaphosphorins; cycloheptaquinolines; cycloheptapyrazines;
cycloheptapyridazines; cycloheptapyrimidines;
cycloheptaoxadiazines; cycloheptathiadiazines;
cycloheptadiazaphosphorins cycloheptaquinoxalines;
cycloheptatriazines; cycloheptathiatriazines; and
cycloheptaoxatriazines.
[0368] N Valence Stabilizer #5a: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tridentates or N--N Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diazacyclopentapyridines; tetraazacyclopentapyridines;
diazacyclopentaquinolines; tetraazacyclopentaquinolines;
diazacyclopentapyrazines; tetraazacyclopentapyrazines;
diazacyclopentapyridazines; tetraazacyclopentapyridazines;
diazacyclopentapyrimidines; tetraazacyclopentapyrimidines;
diazacyclopentatriazines; and tetraazacyclopentatriazines.
[0369] N Valence Stabilizer #5b: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazacycloheptapyridines; tetraazacycloheptapyridines;
diazacycloheptaquinolines; tetraazacycloheptaquinolines;
diazacycloheptapyrazines; tetraazacycloheptapyrazines;
diazacycloheptapyridazines; tetraazacycloheptapyridazines;
diazacycloheptapyrimidines; tetraazacycloheptapyrimidines;
diazacycloheptatriazines; and tetraazacycloheptatriazines.
[0370] N Valence Stabilizer #5c: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
nine binding sites are composed of nitrogen and are contained in a
combination of 6-membered heterocyclic rings and amine or imine
groups (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diazacyclononapyridines; tetraazacyclononapyridines;
diazacyclononaquinolines; tetraazacyclononaquinolines;
diazacyclononapyrazines; tetraazacyclononapyrazines;
diazacyclononapyridazines; tetraazacyclononapyridazines;
diazacyclononapyrimidines; tetraazacyclononapyrimidines;
diazacyclononatriazines; and tetraazacyclononatriazines.
[0371] N Valence Stabilizer #6: Examples of silylamines and
silazanes (N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: trisilylamine;
N-methyldisilazane (disilylmethylamine); N,N-dimethylsilylamine;
(silyldimethylamine); tris(trimethylsilyl)amine; triethylsilylamine
(triethylaminosilane) (triethylsilazane); N-ethyltriethylsilylamine
(triethyl-N-ethylaminosilane); di-tert-butylsilanediamine
(di-tert-butyldiaminosilane); bis(methylamino)diethylsilane;
tris(dimethylamino)ethylsilane; hexamethyldisilazane;
N-methylhexaphenyldisilazane; hexamethylcyclotrisilazane; and
octaphenylcyclotetrasilazane. [Note: Silylamines and silazanes are
notably weaker ligands than their carbonaceous derivatives,
although replacement of one or two SiR.sub.3 groups with CR.sub.3
will enhance the donor power of the ligand. Thus,
N(CR.sub.3).sub.2(SiR.sub.3) is a better ligand than
N(CR.sub.3)(SiR.sub.3).sub.2, etc.]
[0372] N Valence Stabilizer #7: Examples of guanidines,
diguanidines, and polyguanidines (N--N bidentates, N--N
tridentates, N--N tetradentates, and N--N hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
guanidine; methylguanidine; ethylguanidine; isopropylguanidine;
butylguanidine; benzylguanidine; phenylguanidine; tolylguanidine;
naphthylguanidine; cyclohexylguanidine; norbornylguanidine;
adamantylguanidine; dimethylguanidine; diethylguanidine;
diisopropylguanidine; dibutylguanidine; dibenzylguanidine;
diphenylguanidine; ditolylguanidine; dinaphthylguanidine;
dicyclohexylguanidine; dinorbornylguanidine; diadamantylguanidine;
ethylenediguanidine; propylenediguanidine;
tetramethylenediguanidine; pentamethylenediguanidine;
hexamethylenediguanidine; heptamethylenediguanidine;
octamethylenediguanidine; phenylenediguanidine;
piperazinediguanidine; oxalyldiguanidine; malonyldiguanidine;
succinyldiguanidine; glutaryldiguanidine; adipyldiguanidine;
pimelyldiguanidine; suberyldiguanidine; phthalyldiguanidine;
benzimidazoleguanidine; aminoguanidine; nitroaminoguanidine;
dicyandiamide (cyanoguanidine); dodecylguanidine; and nitrovin.
[0373] N Valence Stabilizer #8: Examples of phosphonitrile amides
and bis(phosphonitrile amides) (N--N Bidentates and N--N
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphononitrile amide; N-phenylphosphonitrile
amide; N-benzylphosphonitrile amide; N-cyclohexylphosphonitrile
amide; N-norbornylphosphonitrile amide; N,N'-diphenylphosphonitrile
amide; N,N'-dibenzylphosphonitrile amide;
N,N'-dicyclohexylphosphonitrile amide; and
N,N'-dinorbornylphosphonitrile amide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0374] N Valence Stabilizer #9: Examples of phosphonimidic
diamides, bis(phosphonimidic diamides), and poly(phosphonimidic
diamides) (N--N bidentates and N--N tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphonimidic diamide; N-benzylphosphonimidic diamide;
N-phenylphosphonimidic diamide; N-cyclohexylphosphonimidic diamide;
N-norbornylphosphonimidic diamide; N,N-dibenzylphosphonimidic
diamide; N,N-diphenylphosphonimidic diamide;
N,N-dicyclohexylphosphonimid- ic diamide; and
N,N-dinorbornylphosphonimidic diamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0375] N Valence Stabilizer #10: Examples of phosphonamidimidic
acid, phosphonamidimidothioic acid, bis(phosphonamidimidic acid),
bis(phosphonamidimidothioic acid), poly(phosphonamidimidic acid),
poly(phosphonamidimidothioic acid), and derivatives thereof (N--N
Bidentates, and N--N Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: phosphonamidimidic acid,
phosphonamidimidothioic acid; O-phenylphosphonamidimidic acid;
O-benzylphosphonamidimidic acid; O-cyclohexylphosphonamidimidic
acid; O-orbornylphosphonamidimidic acid;
S-phenylphosphonamidimidothioic acid;
S-enzylphosphonamidimidothioic acid;
S-cyclohexylphosphonamidimidothioic acid; and
S-orbornylphosphonamidimidothioic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0376] Valence Stabilizer #11: Examples of pyridinaldimines,
bis(pyridinaldimines), and poly(pyridinaldimines) (N--N Bidentates,
N--N Tridentates, and N--N Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
pyridylideneaniline [N-(pyridylmethylene)benzenamine]; and
(2-pyridyl)benzylideneaniline.
[0377] N Valence Stabilizer #12: Examples of hydrazones,
bis(hydrazones), and poly(hydrazones) (N Monodentates, N--N
Bidentates, N--N Tridentates, and N--N Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetaldehyde hydrazone; acetaldehyde phenylhydrazone; acetone
hydrazone; acetone phenylhydrazone; pinacolone hydrazone;
pinacolone phenylhydrazone; benzaldehyde hydrazone; benzaldehyde
phenylhydrazone; naphthaldehyde hydrazone; naphthaldehyde
phenylhydrazone; norbornanone hydrazone; norbornanone
phenylhydrazone; camphor hydrazone; camphor phenylhydrazone;
nopinone hydrazone; nopinone phenylhydrazine; 2-pyridinaldehyde
hydrazone; 2-pyridinealdehyde phenylhydrazone; salicylaldehyde
hydrazone; salicylaldehyde phenylhydrazone; quinolinaldehyde
hydrazone; quinolinaldehyde phenylhydrazone; isatin dihydrazone;
isatin di(phenylhydrazone); camphorquinone dihydrazone;
camphorquinone di(phenylhydrazone); and 2-hydrazinobenzimidazole
hydrazone.
[0378] N Valence Stabilizer #13: Examples of azo compounds without
chelate substitution at the ortho- (for aryl) or alpha- or beta-
(for alkyl) positions, bis(azo compounds), or poly(azo compounds)
(N Monodentates, N--N Bidentates, or N--N Tridentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
azobenzene (diphenyldiazene); p-diaminoazobenzene;
p-dimethylaminoazobenzene (butter yellow); methyl orange; Fast
Garnet GBC (4'-amino-2,3'-dimethylazobenzene)[Note: non-bonding
methyl group in the o-position.]; and Alizarin Yellow R. [Note: Azo
compounds without chelate substitution at the ortho- (for aryl) or
beta- (for alkyl) positions tend to stabilize lower oxidation
states in metal ions.]
[0379] N Valence Stabilizer #14: Examples of formazans,
bis(formazans), and poly(formazans) without ortho- hydroxy,
carboxy, thiol, mercapto, amino, or hydrazido substitution (N--N
Bidentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
1,3,5-triphenylformazan; and 1,3,5-naphthylformazan.
[0380] N Valence Stabilizer #15: Examples of hydramides (N--N
Bidentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hydrobenzamide; hydronaphthamide; and
hydrosalicylamide.
[0381] N Valence Stabilizer #16: Examples of azines (including
ketazines), bis(azines), and poly(azines) without ortho-hydroxy,
carboxy, thiol, mercapto, amino, or hydrazido substitution (N--N
Bidentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
benzalazine; napbthalazine; cyclohexanonazine; and
norbornonazine.
[0382] N Valence Stabilizer #17: Examples of Schiff Bases with one
Imine (C.dbd.N) Group and without ortho- (for aryl constituents) or
alpha- or beta- (for alkyl constituents) hydroxy, carboxy,
carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo,
diazeno, or hydrazido substitution (N Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N-(Benzaldehydo)isopropylamine; N-(Naphthaldehydo)isopropylamine;
N-(Acetophenono)isopropyl amine; N-(Propiophenono)isopropylamine;
N-(Benzaldehydo)cyclohexylamine; N-(Naphthaldehydo)cyclohexylamine;
N-(Acetophenono)cyclohexylamine; N-(Propiophenono)cyclohexylamine;
N-(Benzaldehydo)aniline (BAAN); N-(Naphthaldehydo)aniline;
N-(Acetophenono)aniline; N-(Propiophenono)aniline;
N-(Benzaldehydo)aminonorbornane; N-(Naphthaldehydo)aminonorbornane;
N-(Acetophenono)aminonorbornane; N-(Propiophenono)aminonorbornane;
(Vanillino)anisidine; (Cinnamaldehydo)anisidine;
N-(o-carboxycinnamaldehydo)aniline; N-(cinnamaldehydo)aniline;
N-(cinnamaldehydo)m- or p-anisidine; and
N-(o-carboxycinnamaldehydo)m- or p-anisidine.
[0383] N Valence Stabilizer #18: Examples of isocyanide and
cyanamide and related ligands (N Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
isocyanate (--NCO); isothiocyanate (--NCS); isoselenocyanate
(--NCSe); and cyanamide (--NCN). [Note: the nitrogen atom is
directly complexed to the high valence metal ion.]
[0384] N Valence Stabilizer #19: Examples of nitrosyls and nitrites
and related ligands (N Monodentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: nitrosyl (--NO);
thionitrosyl (--NS); nitrite (--NO.sub.2); thionitrite
(sulfinylamide)(thiazate)(--NSO); nitrosamine (.dbd.NN.dbd.O);
thionitrosamine (NN.dbd.S); nitramine (.dbd.NNO.sub.2); and
thionitramine (.dbd.NNS.sub.2) ligands.
[0385] N Valence Stabilizer #20: Examples of nitriles, dinitriles,
and polynitriles (N Monodentates, N--N Bidentates, N--N
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: benzonitrile; naphthonitrile; cyanonaphthalene;
cyclohexyl nitrile; cyanopyridine; cyanopurine; cyanophenol;
cyanothiophenol; adamantane nitrile; norbornyl nitrile;
cinnamonitrile; dicyanobenzene; dicyanobutene; dicyanoimidazole;
dicyanopyridine; cyanotolunitrile; tetracyanoethylene (TCNE);
tetracyanoquinodimethane (TCNQ); diethylaminopropionitrile (deapn),
and polyacrylonitriles.
[0386] N Valence Stabilizer #21: Examples of azide ligands (N
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: azide (--N.sub.3) ions; methyl azide; ethyl azide;
phenyl azide; diphenyltriazene; and phenyl sulfonyl azide.
[0387] S Valence Stabilizer #1: Examples of monothioethers (S
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hydrogen sulfide, dimethyl sulfide, diethyl
sulfide, dioctyl sulfide, diphenyl sulfide, dicyclohexyl sulfide,
tetramethylene sulfide (tetrahydrothiophene, tht), trimethylene
sulfide, dimethylene sulfide (ethylene sulfide), pentamethylene
sulfide, 1,4-thioxane, oxathiolane, cyclohexene sulfide,
cyclooctene sulfide, benzotetrahydrothiophene, dibenzothiophene,
naphthotetrahydrothiophene, and thiabicycloheptane.
[0388] S Valence Stabilizer #2: Examples of disulfides (S
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: methyl disulfide, ethyl disulfide, phenyl
disulfide, nitrophenide, and 1,2-dithiacyclohexane.
[0389] S Valence Stabilizer #3: Examples of dithioethers (S
monodentates or S--S bidentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: 1,3-dithiane, 1,4-dithiane,
benzodithiane, dibenzodithiane, naphthodithiane, 2,5-dithiahexane
(dth); 3,6-dithiaoctane (dto); 2,5-dimethyl-3,6-dithiaoctane;
3,7-dithianonane; 2,6-dithiaheptane; 1,6-diphenyl-2,5-dithiahexane;
1,4-dipbenyl-1,4-dithiabutane; 1,3-dithiolane; 1,4-dithiane
(1,4-dithiacyclohexane); 1,4-dithiacycloheptane (dtch);
1,5-dithiacyclooctane (dtco); o-phenylenebis(2-thiapropane);
o-phenylenebis(2-thiabutane); 2,2'-(thiamethyl)biphenyl, and
2,2'-(thiaethyl)biphenyl.
[0390] S Valence Stabilizer #4: Examples of trithioethers (S
monodentates, S--S bidentates, or S--S tridentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
1,3,5-trithiane; 1,3,5-tris(methylthia)c- yclohexane;
1,3,5-tris(ethylthia)cyclohexane; 1,3,5-tris(phenylthia)cycloh-
exane; 2,5,8-trithianonane; 3,6,9-trithiaundecane; and
2,6,10-trithiaundecane.
[0391] S Valence Stabilizer #5: Examples of tetrathioetbers (S
monodentates, S--S bidentates, S--S tridentates, or S--S
tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 1,4,10,13-tetrathiatridecane;
2,6,10,14-tetrathiapentadecane; 2,5,8,11-tetrathiadodecane;
2,5,9,12-ttetrathiatridecane; 2,6,9,13-tetrathiatetradecane;
1,4-(o-thiomethyl)phenyl-1,4-dithiabutane;
1,5-(o-thiomethyl)phenyl-1,5-dithiapentane;
1,6-(o-thiomethyl)phenyl-1,6-- dithiahexane;
1,4-(o-thiomethyl)phenyl-1,4-dithiabut-2-ene; and
polythioethers.
[0392] S Valence Stabilizer #6: Examples of hexathioethers (S
monodentates, S--S bidentates, S--S tridentates, S--S
tetradentates, or S--S hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
tri(2-((o-thiomethyl)phenyl)ethyl)amine; and
tri((o-thiomethyl)phenyl)methylamine.
[0393] S Valence Stabilizer #7a: Examples of 5-membered
heterocyclic rings containing one sulfur atom (S monodentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dihydrothiophene, thiophene, thiazole, thiapyrroline,
thiaphospholene, thiaphosphole, oxathiole, thiadiazole,
thiatriazole, benzodihydrothiophene, benzothiophene, benzothiazole,
benzothiaphosphole, dibenzothiophene, and naphthothiophene.
[0394] S Valence Stabilizer #7b: Examples of 5-membered
heterocyclic rings containing two sulfur atoms (S monodentates or
S--S bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiole, benzodithiole, and
naphthodithiole.
[0395] S Valence Stabilizer #8a: Examples of 6-membered
heterocyclic rings containing one sulfur atom (S monodentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dihydrothiopyran, thiopyran, thiazine, thiadiazine, thiaphosphorin,
thiadiphosphorin, oxathiin, benzothiopyran, dibenzothiopyran, and
naphthothiopyran.
[0396] S Valence Stabilizer #8b: Examples of 6-membered
heterocyclic rings containing two sulfur atoms (S monodentates or
S--S bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dihydrodithiin, dithiin, benzodithiin,
dibenzodithiin (thianthrene), and naphthodithiin.
[0397] S Valence Stabilizer #9a: Examples of 5-membered
heterocyclic rings containing one sulfur atom and having at least
one additional sulfur atom binding site not contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2,5-dimercapto-2,5-dihy-
drothiophene; 2,5-bis(thiomethyl)-2,5-dihydrothiophene;
2,5-bis(2-thiophenyl)-2,5-dihydrothiophene;
2,5-dimercaptothiophene; 2,5-bis(thiomethyl)thiophene;
2,5-bis(2-thiophenyl)thiophene; 2,5-dimercatothiazole;
2,5-bis(thiomethyl)thiazole; 2,5-bis(2-thiophenyl)thiazole;
2,5-dimercapto-1,3,4-thiadiazole [bismuththiol];
2-mercaptothianaphthene; 7-(thiomethyl)thianaphthene;
1,8-dimercaptodibenzothiophene; 2-mercaptobenzothiazole;
2-mercapro-1,3,4-thiadiazole; 2-amino-5-mercapto-1,3,4-thiadiazole;
2,5-bis(alkylthio)-1,3,4-thiadiazole; and
7-(thiomethyl)benzothiazole.
[0398] S Valence Stabilizer #9b: Examples of 5-membered
heterocyclic rings containing two sulfur atoms and having at least
one additional sulfur atom binding site not contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-mercapto-1,3-dithiole;
2-(dimercaptomethyl)-1,3-dithiole; 4,5-dimercapto-1,3-dithiole;
4,5-bis(2-thiophenyl)-1,3-dithiole; 2-mercaptobenzodithiole; and
7-mercaptobenzodithiole.
[0399] S Valence Stabilizer #10a: Examples of 6-membered
heterocyclic rings containing one sulfur atom and having at least
one additional sulfur atom binding site not contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,6-dimercapto-2,5-dihydrothiopyran;
2,6-bis(thiomethyl)-2,5-dihydrothiop- yran;
2,6-bis(2-thiophenyl)-2,5-dihydrothiopyran;
2,6-dimercaptothiopyran; 2,6-bis(thiomethyl)thiopyran;
2,6-bis(2-thiophenyl)thiopyran; 2,6-dimercaptothiazine;
2,6-bis(thiomethyl)thiazine; 2,6-bis(2-thiophenyl)thiazine;
2,6-dimercapto-1,3,5-thiadiazine; 2-mercapto-1-benzothiopyran;
8-mercapto-1-benzothiopyran; and
1,9-dimercaptodibenzothiopyran.
[0400] S Valence Stabilizer #10b: Examples of 6-membered
heterocyclic rings containing two sulfur atoms and having at least
one additional sulfur atom binding site not contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-mercapto-1,4-dithiin;
2,6-dimercapto-1,4-dithiin; 2,6-bis(2-thiophenyl)-1,4-dithiin;
2,3-dimercapto-1,4-benzodithiin; 5,8-dimercapto-1,4-benzodithiin;
1,8-dimercaptothianthrene; and
1,4,5,8-tetramercaptothianthrene.
[0401] S Valence Stabilizer #11a: Examples of 5-membered
heterocyclic rings containing one sulfur atom and having at least
one additional sulfur atom binding site contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-2,5-dihydrothio- phene;
2,2',2"-tri-2,5-dihydrothiophene; 2,2'-bithiophene;
2,2',2"-trithiophene; 2,2'-bithiazole; 5,5'-bithiazole;
2,2'-bioxathiole; 2,2'-bi-1,3,4-thiadiazole; 2,2'-bithianaphthene;
2,2'-bibenzothiazole; 1,1'-bis(dibenzothiophene); and
polythiophenes.
[0402] S Valence Stabilizer #11b: Examples of 5-membered
heterocyclic rings containing two sulfur atoms and having at least
one additional sulfur atom binding site contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1,3-dithiole; 4,4'-bi-1,3-dithiole;
7,7'-bi-1,2-benzodithiole; 3,3'-bi-1,2-benzodithiol- e; and
tetrathiofulvalene.
[0403] S Valence Stabilizer #12a: Examples of 6-membered
heterocyclic rings containing one sulfur atom and having at least
one additional sulfur atom binding site contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-2,5-dihydrothio- pyran;
2,2',2"-tri-2,5-dihydrothiopyran; 2,2'-bithiopyran;
2,2',2"-trithiopyran; 2,2'-bi-1,4-thiazine;
2,2'-bi-1,3,5-thiadiazine; 2,2'-bi-1-benzothiopyran; and
1,1'-bis(dibenzothiopyran)
[0404] S Valence Stabilizer #12b: Examples of 6-membered
heterocyclic rings containing two sulfur atoms and having at least
one additional sulfur atom binding site contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1,4-dithiin; 2,2'-bi-1,3-dithiin;
5,5'-bi-1,4-benzodithiin; 2,2'-bi-1,3-benzodithiin; and
1,1'-bithianthrene.
[0405] S Valence Stabilizer #13a: Examples of two-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein both
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Bidentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiacyclobutane ([4]aneS.sub.2);
dithiacyclopentane ([5]aneS.sub.2); dithiacyclohexane
([6]aneS.sub.2); dithiacycloheptane ([7]aneS.sub.2);
dithiacyclooctane ([8]aneS.sub.2); dithiacyclobutene
([4]cneS.sub.2); dithiacyclopentene ([5]eneS.sub.2);
dithiacyclohexene ([6]eneS.sub.2); dithiacycloheptene
([7]eneS.sub.2); dithiacyclooctene ([8]eneS.sub.2);
dithiacyclobutadiene ([4]dieneS.sub.2); dithiacyclopentadiene
([5]dieneS.sub.2); dithiacyclohexadiene ([6]dieneS.sub.2);
dithiacycloheptadiene ([7]dieneS.sub.2); and dithiacyclooctadiene
([8]dieneS.sub.2).
[0406] S Valence Stabilizer #13b: Examples of three-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: trithiacyclohexane ([6]aneS.sub.3);
trithiacycloheptane ([7]aneS.sub.3); trithiacyclooctane
([8]aneS.sub.3); trithiacyclononane ([9]aneS.sub.3);
trithiacyclodecane ([10]aneS.sub.3); trithiacycloundecane
([11]aneS.sub.3); trithiacyclododecane ([12]aneS.sub.3);
trithiacyclohexene ([6]eneS.sub.3); trithiacycloheptene
([7]eneS.sub.3); trithiacyclooctene ([8]eneS.sub.3);
trithiacyclononene ([9]eneS.sub.3); trithiacyclodecene
([10]eneS.sub.3); trithiacycloundecene ([11]eneS.sub.3);
trithiacyclododecene ([12]eneS.sub.3); trithiacyclohexatriene
([6]trieneS.sub.3); trithiacycloheptatriene ([7]trieneS.sub.3);
trithiacyclooctatriene ([8]trieneS.sub.3); trithiacyclononatriene
([9]trieneS.sub.3); trithiacyclodecatriene ([10]trieneS.sub.3);
trithiacycloundecatriene ([11]trieneS.sub.3); and
trithiacyclododecatrien- e ([12]trieneS.sub.3).
[0407] S Valence Stabilizer #13c: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tetrathiacyclooctane ([8]aneS.sub.4);
tetrathiacyclononane ([9]aneS.sub.4); tetrathiacyclodecane
([10]aneS.sub.4); tetrathiacycloundecane ([11]aneS.sub.4);
tetrathiacyclododecane ([12]aneS.sub.4); tetrathiacyclotridecane
([13]aneS.sub.4); tetrathiacyclotetradecane ([14]aneS.sub.4);
tetrathiacyclopentadecane ([15]aneS.sub.4);
tetrathiacyclohexadecane ([16]aneS.sub.4);
tetrathiacycloheptadecane ([17]aneS.sub.4);
tetrathiacyclooctadecane ([18]aneS.sub.4); tetrathiacyclononadecane
([19]aneS.sub.4); tetrathiacycloeicosane ([20]aneS.sub.4);
tetrathiacyclooctadiene ([8]dieneS.sub.4); tetrathiacyclononadiene
([9]dieneS.sub.4); tetrathiacyclodecadiene ([10]dieneS.sub.4);
tetrathiacycloundecadiene ([11]dieneS.sub.4);
tetrathiacyclododecadiene ([12]dieneS.sub.4);
tetrathiacyclotridecadiene ([13]dieneS.sub.4);
tetrathiacyclotetradecadiene ([14]dieneS.sub.4);
tetrathiacyclopentadecadiene ([15]dieneS.sub.4);
tetrathiacyclohexadecadi- ene ([16]dieneS.sub.4);
tetrathiacycloheptadecadiene ([17]dieneS.sub.4);
tetrathiacyclooctadecadiene ([18]dieneS.sub.4);
tetrathiacyclononadecadie- ne ([19]dieneS.sub.4);
tetrathiacycloeicosadiene ([20]dieneS.sub.4);
tetrathiacyclooctatetradiene ([8]tetradieneS.sub.4);
tetrathiacyclononatetradiene ([9]tetradieneS.sub.4);
tetrathiacyclodecatetradiene ([10]tetradieneS.sub.4);
tetrathiacycloundecatetradiene ([11]tetradieneS.sub.4);
tetrathiacyclododecatetradiene ([12]tetradieneS.sub.4);
tetrathiacyclotridecatetradiene ([13]tetradieneS.sub.4);
tetrathiacyclotetradecatetradiene ([14]tetradieneS.sub.4);
tetrathiacyclopentadecatetradiene ([15]tetradieneS.sub.4);
tetrathiacyclohexadecatetradiene ([16]tetradieneS.sub.4);
tetrathiacycloheptadecatetradiene ([17]tetradieneS.sub.4);
tetrathiacyclooctadecatetradiene ([18]tetradieneS.sub.4);
tetrathiacyclononadecatetradiene ([19]tetradieneS.sub.4); and
tetrathiacycloeicosatetradiene ([20]tetradieneS.sub.4).
[0408] S Valence Stabilizer #13d: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates or S--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: pentathiacyclodecane
([10]aneS.sub.5); pentathiacycloundecane ([11]aneS.sub.5);
pentathiacyclododecane ([12]aneS.sub.5); pentathiacyclotridecane
([13]aneS.sub.5); pentathiacyclotetradecane ([14]aneS.sub.5);
pentathiacyclopentadecane ([15]aneS.sub.5);
pentathiacyclodecatriene ([10]trieneS.sub.5);
pentathiacycloundecatriene ([11]trieneS.sub.5);
pentathiacyclododecatriene ([12]trieneS.sub.5);
pentathiacyclotridecatriene ([13]trieneS.sub.5);
pentathiacyclotetradecat- riene ([14]trieneS.sub.5); and
pentathiacyclopentadecatriene ([15]trieneS.sub.5).
[0409] S Valence Stabilizer #13e: Examples of six-membered
macrocyclics,-macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexathiacyclododecane ([12]aneS.sub.6); hexathiacyclotridecane
([13]aneS.sub.6); hexathiacyclotetradecane ([14]aneS.sub.6);
hexathiacyclopentadecane ([15]aneS.sub.6); hexathiacyclohexadecane
([16]aneS.sub.6); hexathiacycloheptadecane ([17]aneS.sub.6);
hexathiacyclooctadecane ([18]aneS.sub.6); hexathiacyclononadecane
([19]aneS.sub.6); hexathiacycloeicosane ([20]aneS.sub.6);
hexathiacycloheneicosane ([21]aneS.sub.6); hexathiacyclodocosane
([22]aneS.sub.6); hexathiacyclotricosane ([23]aneS.sub.6);
hexathiacyclotetracosane ([24]aneS.sub.6);
hexathiacyclododecatriene ([12]trieneS.sub.6);
hexathiacyclotridecatriene ([13]trieneS.sub.6);
hexathiacyclotetradecatriene ([14]trieneS.sub.6);
hexathiacyclopentadecatriene ([15]trieneS.sub.6);
hexathiacyclohexadecatr- iene ([16]trieneS.sub.6);
hexathiacycloheptadecatriene ([17]trieneS.sub.6);
hexathiacyclooctadecatriene ([18]trieneS.sub.6);
hexathiacyclononadecatriene ([19]trieneS.sub.6);
hexathiacycloeicosatrien- e ([20]trieneS.sub.6);
hexathiacycloheneicosatriene ([21]trieneS.sub.6);
hexathiacyclodocosatriene ([22]trieneS.sub.6);
hexathiacyclotricosatriene ([23]trieneS.sub.6); and
hexathiacyclotetracosatriene ([24]trieneS.sub.6).
[0410] S Valence Stabilizer #13f: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
heptathiacyclotetradecane ([14]aneS.sub.7);
heptathiacyclopentadecane ([15]aneS.sub.7);
heptathiacyclohexadecane ([16]aneS.sub.7);
heptathiacycloheptadecane ([17]aneS.sub.7);
heptathiacyclooctadecane ([18]aneS.sub.7); heptathiacyclononadecane
([19]aneS.sub.7); heptathiacycloeicosane ([20]aneS.sub.7);
heptathiacycloheneicosane ([21]aneS.sub.7);
heptathiacyclotetradecatriene ([14]trieneS.sub.7);
heptathiacyclopentadecatriene ([15]trieneS.sub.7);
heptathiacyclohexadecatriene ([16]trieneS.sub.7);
heptathiacycloheptadeca- triene ([17]trieneS.sub.7);
heptathiacyclooctadecatriene ([18]trieneS.sub.7);
heptathiacyclononadecatri ene ([19]trieneS.sub.7);
heptathiacycloeicosatriene ([20]trieneS.sub.7); and
heptathiacycloheneicosatriene ([21]trieneS.sub.7).
[0411] S Valence Stabilizer #13g: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
octathiacyclohexadecane ([16]aneS.sub.8); octathiacycloheptadecane
([17]aneS.sub.8); octathiacyclooctadecane ([18]aneS.sub.8);
octathiacyclononadecane ([19]aneS.sub.8); octathiacycloeicosane
([20]aneS.sub.8); octathiacycloheneicosane ([21]aneS.sub.8);
octathiacyclodocosane ([22]aneS.sub.8); octathiacyclotricosane
([23]aneS8); octathiacyclotetracosane ([24]aneS.sub.8);
octathiacyclohexadecatetradiene ([16]tetradieneS.sub.8)- ;
octathiacycloheptadecatetradiene ([17]tetradieneS.sub.8);
octathiacyclooctadecatetradiene ([18]tetradieneS.sub.8);
octathiacyclononadecatetradiene ([19]tetradieneS.sub.8);
octathiacycloeicosatetradiene ([20]tetradieneS.sub.8);
octathiacycloheneicosatetradiene ([21]tetradieneS.sub.8);
octathiacyclodocosatetradiene ([22]tetradieneS.sub.8);
octathiacyclotricosatetradiene ([23]tetradieneS.sub.8); and
octathiacyclotetracosatetradiene ([24]tetradieneS.sub.8).
[0412] S Valence Stabilizer #13h: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
nonathiacyclooctadecane ([18]aneS.sub.9); nonathiacyclononadecane
([19]aneS.sub.9); nonathiacycloeicosane ([20]aneS.sub.9);
nonathiacycloheneicosane ([21]aneS.sub.9); nonathiacyclodocosane
([22]aneS.sub.9); nonathiacyclotricosane ([23]aneS.sub.9);
nonathiacyclotetracosane ([24]aneS.sub.9); nonathiacyclopentacosane
([25]aneS.sub.9); nonathiacyclohexacosane ([26]aneS.sub.9);
nonathiacycloheptacosane ([27]aneS.sub.9);
nonathiacyclooctadecatetradiene ([18]tetradieneS.sub.9);
nonathiacyclononadecatetradiene ([19]tetradieneS.sub.9);
nonathiacycloeicosatetradiene ([20]tetradieneS.sub.9);
nonathiacycloheneicosatetradiene ([21]tetradieneS.sub.9);
nonathiacyclodocosatetradiene ([22]tetradieneS.sub.9);
nonathiacyclotricosatetradiene ([23]tetradieneS.sub.9);
nonathiacyclotetracosatetradiene ([24]tetradieneS.sub.9);
nonathiacyclopentacosatetradiene ([25]tetradieneS.sub.9);
nonathiacyclohexacosatetradiene ([26]tetradieneS.sub.9); and
nonathiacycloheptacosatetradiene ([27]tetradieneS.sub.9).
[0413] S Valence Stabilizer #13i: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol or thioether
groups) and are not contained in component heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
decathiacycloeicosane ([20]aneS.sub.10); decathiacycloheneicosane
([21]aneS.sub.10); decathiacyclodocosane ([22]aneS.sub.10);
decathiacyclotricosane ([23]aneS.sub.10); decathiacyclotetracosane
([24]aneS.sub.10); decathiacyclopentacosane ([25]aneS.sub.10);
decathiacyclohexacosane ([26]aneS.sub.10); decathiacycloheptacosane
([27]aneS.sub.10); decathiacyclooctacosane ([28]aneS.sub.10);
decathiacyclononacosane ([29]aneS.sub.10); decathiacyclotriacontane
([30]aneS.sub.10); decathiacycloeicosapentadiene
([20]pentadieneS.sub.10); decathiacycloheneicosapentadiene
([21]pentadieneS.sub.10); decathiacyclodocosapentadiene
([22]pentadieneS.sub.10); decathiacyclotricosapentadiene
([23]pentadieneS.sub.10); decathiacyclotetracosapentadiene
([24]pentadieneS.sub.10); decathiacyclopentacosapentadiene
([25]pentadieneS.sub.10); decathiacyclohexacosapentadiene
([26]pentadieneS.sub.10); decathiacycloheptacosapentadiene
([27]pentadieneS.sub.10); decathiacyclooctacosapentadiene
([28]pentadieneS.sub.10); decathiacyclononacosapentadiene
([29]pentadieneS.sub.10); and decathiacyclotriacontapentadiene
([30]pentadieneS.sub.10).
[0414] S Valence Stabilizer #14a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetrathiophenes; tetrathiazoles; tetrathiaphospholes;
tetraoxathioles; tetrathiadiazoles; tetrathiatriazoles; and
tetradithioles.
[0415] S Valence Stabilizer #14b: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tridentates or S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: pentathiophenes; pentathiazoles;
pentathiaphospholes; pentaoxathioles; pentathiadiazoles;
pentathiatriazoles; and pentadithioles.
[0416] S Valence Stabilizer #14c: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: hexathiophenes;
hexathiazoles; hexathiaphospholes; hexaoxathioles;
hexathiadiazoles; hexathiatriazol es; and hexadithioles.
[0417] S Valence Stabilizer #14d: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: heptathiophenes;
heptathiazoles; heptathiaphospholes; heptaoxathioles;
heptathiadiazoles; heptathiatriazoles; and heptadithioles.
[0418] S Valence Stabilizer #14e: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: octathiophenes;
octathiazoles; octathiaphospholes; octaoxathioles;
octathiadiazoles; octathiatriazoles; and octadithioles.
[0419] S Valence Stabilizer #14f: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
nine binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: nonathiophenes;
nonathiazoles; nonathiaphospholes; nonaoxathioles;
nonathiadiazoles; nonathiatriazoles; and nonadithioles.
[0420] S Valence Stabilizer #14g: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of sulfur and are contained in
component 5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn
include, but are not limited to: decathiophenes; decathiazoles;
decathiaphospholes; decaoxathioles; decathiadiazoles;
decathiatriazoles; and decadithioles.
[0421] S Valence Stabilizer #15a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: dithiatetrathiophenes;
tetrathiatetrathiophenes; dithiatetradithioles; and
tetrathiatetradithioles.
[0422] S Valence Stabilizer #15b: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates or S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithiapentathiophenes; tetrathiapentathiophenes;
dithiapentadithioles; and tetrathiapentadithioles.
[0423] S Valence Stabilizer #15c: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiahexaathiophenes; trithiahexathiophenes;
dithiahexadithioles; and trithiahexadithioles.
[0424] S Valence Stabilizer #15d: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiaheptathiophenes; tetrathiaheptathiophenes;
dithiaheptadithioles; and tetrathiaheptadithioles.
[0425] S Valence Stabilizer #15e: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiaoctathiophenes; tetrathiaoctathiophenes;
dithiaoctadithioles; and tetrathiaoctadithioles.
[0426] S Valence Stabilizer #15f: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
nine binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: trithianonathiophenes; hexathianonathiophenes;
trithianonadithioles; and hexathianonadithioles.
[0427] S Valence Stabilizer #15g: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of sulfur and are contained in a
combination of 5-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiadecathiophenes; pentathiadecathiophenes;
dithiadecadithioles; and pentathiadecadithioles.
[0428] S Valence Stabilizer #16a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetrathiopyrans; tetrathiazines; tetrathiaphosphorins;
tetrathiadiphosphorins; tetraoxathiins; and tetradithiins.
[0429] S Valence Stabilizer #16b: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates or S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: pentathiopyrans; pentathiazines;
pentathiaphosphorins; pentathiadiphosphorins; pentaoxathiins; and
pentadithins.
[0430] S Valence Stabilizer #16c: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: hexathiopyrans;
hexathiazines; hexathiaphosphorins; hexathiadiphosphorins;
hexaoxathiins; and hexadithiins.
[0431] S Valence Stabilizer #16d: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: heptathiopyrans;
heptathiazines; heptathiaphosphorins; heptathiadiphosphorins;
heptaoxathiins; and heptadithiins.
[0432] S Valence Stabilizer #16e: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: octathiopyrans;
octathiazines; octathiaphosphorins; octathiadiphosphorins;
octaoxathiins; and octadithiins.
[0433] S Valence Stabilizer #16f: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
nine binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+ include, but are not limited to: nonathiopyrans;
nonathiazines; nonathiaphosphorins; nonathiadiphosphorins;
nonaoxathiins; and nonadithiins.
[0434] S Valence Stabilizer #16g: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: decathiopyrans;
decathiazines; decatbiaphosphorins; decathiadiphosphorins;
decaoxathiins; and decadithiins.
[0435] S Valence Stabilizer #17a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: dithiatetrathiopyrans;
tetrathiatetrathiopyrans; dithiatetrathiazines;
tetrathiatetrathiazines; dithiatetrathiaphosphorins;
tetrathiatetrathiaphosphorins; dithiatetraoxathiins;
tetrathiatetraoxathiins; dithiatetradithiins; and
tetrathiatetradithiins.
[0436] S Valence Stabilizer #17b: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
five binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates or S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithiapentathiopyrans; tetrathiapentathiopyrans;
dithiapentathiazines; tetrathiapentathiazines;
dithiapentathiaphosphorins- ; tetrathiapentathiaphosphorins;
dithiapentaoxathiins; tetrathiapentaoxathiins; dithiapentadithiins;
and tetrathiapentadithiins.
[0437] S Valence Stabilizer #17c: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiahexathiopyrans; trithiahexathiopyrans;
dithiahexathiazines; trithiahexathiazines;
dithiahexathiaphosphorins; trithiahexathiaphosphorins;
dithiahexaoxathiins; trithiahexaoxathiins; dithiahexadithiins; and
trithiahexadithiins.
[0438] S Valence Stabilizer #17d: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiaheptathiopyrans; tetrathiaheptathiopyrans;
dithiaheptathiazines; tetrathiaheptathiazines;
dithiaheptathiaphosphorins; tetrathiaheptathiaphosphorins;
dithiaheptaoxathiins; tetrathiaheptaoxathiins; dithiaheptadithiins;
and tetrathiaheptadithiins.
[0439] S Valence Stabilizer #17e: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiaoctathiopyrans; tetrathiaoctathiopyrans;
dithiaoctathiazines; tetrathiaoctathiazines;
dithiaoctathiaphosphorins; tetrathiaoctathiaphosphorins;
dithiaoctaoxathiins; tetrathiaoctaoxathiins; dithiaoctadithiins;
and tetrathiaoctadithiins.
[0440] S Valence Stabilizer #17f: Examples of nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
nine binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: trithianonathiopyrans; hexathianonathiopyrans;
trithianonathiazines; hexathianonathiazines;
trithianonathiaphosphorins; hexathianonathiaphosphorins;
trithianonaoxathiins; hexathianonaoxathiins; trithianonadithiins;
and hexathianonadithiins.
[0441] S Valence Stabilizer #17g: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
ten binding sites are composed of sulfur and are contained in a
combination of 6-membered heterocyclic rings and thiol, thioether,
or thioketo groups (S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiadecathiopyrans; pentathiadecathiopyrans;
dithiadecathiazines; pentathiadecathiazines;
dithiadecathiaphosphorins; pentathiadecathiaphosphorins;
dithiadecaoxathiins; pentathiadecaoxathiins; dithiadecadithins; and
pentathiadecadithiins.
[0442] S Valence Stabilizer #18: Examples of dithiobiurets
(dithioimidodicarbonic diamides), dithioisobiurets, dithiobiureas,
trithiotriurets, trithiotriureas, bis(dithiobiurets),
bis(dithioisobiurets), bis(dithiobiureas), poly(dithiobiurets),
poly(dithioisobiurets), and poly(dithiobiureas) (S--S Bidentates,
S--S Tridentates, S--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: dithiobiuret,
dithioisobiuret, dithiobiurea, trithiotriuret, trithiotriurea,
nitrodithiobiuret, dinitrodithiobiuret, aminodithiobiuret,
diaminodithiobiuret, oxydithiobiuret, dioxydithiobiuret,
cyanodithiobiuret, methyldithiobiuret, ethyldithiobiuret,
isopropyldithiobiuret, phenyldithiobiuret, benzyldithiobiuret,
cyclohexyldithiobiuret, norbornyldithiobiuret,
adamantyldithiobiuret, dimethyldithiobiuret, diethyldithiobiuret,
diisopropyldithiobiuret, diphenyldithiobiuret,
dibenzyldithiobiuret, dicyclohexyldithiobiuret,
dinorbornyldithiobiuret, and diadamantyldithiobiuret.
[0443] S Valence Stabilizer #19: Examples of thioacylthioureas,
thioaroylthioureas, bis(thioacylthioureas),
bis(thioaroylthioureas), poly(thioacylthioureas), and
poly(thioaroylthioureas) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: thioformylthiourea, thioacetylthiourea,
thiobenzoylthiourea, thiocyclohexoylthiourea,
pentafluorothiobenzoylthiou- rea, N-methylthioacetylthiourea,
N-phenylthiobenzoylthiourea, and
N-cyclohexylthiocyclohexoylthiourea.
[0444] S Valence Stabilizer #20: Examples of dithioacyl disulfides,
bis(dithioacyl disulfides), and poly(dithioacyl disulfides), (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithioacetyl disulfide; dithiopropanoyl disulfide; dithiobenzoyl
disulfide; and dithiopentafluorobenzoyl disulfide.
[0445] S Valence Stabilizer #21: Examples of
tetrathioperoxydicarbonic diamides, bis(tetrathioperoxydicarbonic
diamides), and poly(tetrathioperoxydicarbonic diamides) (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetrathioperoxydicarbonic diamide;
N-phenyltetrathioperoxydicarbonic diamide;
N-benzyltetrathioperoxydicarbo- nic diamide;
N-cyclohexyltetrathioperoxydicarbonic diamide;
N-norbornyltetrathioperoxydicarbonic diamide;
N,N'-diphenyltetrathioperox- ydicarbonic diamide;
N,N'-dibenzyltetrathioperoxydicarbonic diamide;
N,N'-dicyclohexyltetrathioperoxydicarbonic diamide; and
N,N'-dinorbornyltetrathioperoxydicarbonic diamide.
[0446] S Valence Stabilizer #22: Examples of hexathio-, pentathio-,
and tetrathioperoxydicarbonic acids, bis(hexathio-, pentathio-, and
tetrathioperoxydicarbonic acids), poly(hexathio-, pentathio-, and
tetrathioperoxydicarbonic acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexathioperoxydicarboni- c acid, pentathioperoxydicarbonic acid,
tetrathioperoxydicarbonic acid, S-phenylhexathioperoxydicarbonic
acid; S-benzylhexathioperoxydicarbonic acid;
S-cyclohexylhexathioperoxydicarbonic acid;
S-norbornylhexathioperox- ydicarbonic acid;
S,S'-diphenylhexathioperoxydicarbonic acid;
S,S'dibenzylhexathioperoxydicarbonic acid;
S,S'-dicyclohexylhexathioperox- ydicarbonic acid; and
S,S'-dinorbornylhexathioperoxydicarbonic acid.
[0447] S Valence Stabilizer #23: Examples of
dithioperoxydiphosphoramides, bis(dithioperoxydiphosphoramides),
and poly(dithioperoxydiphosphoramides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: dithioperoxydiphosphora- mide,
N-methyldithioperoxydiphosphoramide,
N-isopropyldithioperoxydiphosph- oramide,
N-tert-butyldithioperoxydiphosphoramide, N-phenyldithioperoxydiph-
osphoramide, N-pentafluorophenyldithioperoxydiphosphoramide,
N-benzyldithioperoxydiphosphoramide,
N-cyclohexyldithioperoxydiphosphoram- ide,
N-norbornyldithioperoxydiphosphoramide,
N,N'"-dimethyldithioperoxydip- hosphoramide,
N,N'"-diisopropyldithioperoxydiphosphoramide,
N,N'"-di-tert-butyldithioperoxydiphosphoramide,
N,N'"-diphenyldithioperox- ydiphosphoramide,
N,N'"-di-pentafluorophenyldithioperoxydiphosphoramide,
N,N'"-dibenzyldithioperoxydiphosphoramide,
N,N'"-dicyclohexyldithioperoxy- diphosphoramide, and
N,N'"-dinorbornyldithioperoxydiphosphoramide.
[0448] S Valence Stabilizer #24: Examples of
dithioperoxydiphosphoric acids, bis(dithioperoxydiphosphoric
acids), poly(dithioperoxydiphosphoric acids), and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: dithioperoxydiphosphoric acid,
methyldithioperoxydiphospboric acid,
isopropyldithioperoxydiphosphoric acid,
tert-butyldithioperoxydipho- sphoric acid,
phenyldithioperoxydiphosphoric acid, pentafluorophenyldithio-
peroxydiphosphoric acid, benzyldithioperoxydiphosphoric acid,
cyclohexyldithioperoxydiphosphoric acid,
norbornyldithioperoxydiphosphori- c acid,
dimethyldithioperoxydiphosphoric acid, diisopropyldithioperoxydiph-
osphoric acid, di-tert-butyldithioperoxydiphosphoric acid,
diphenyldithioperoxydiphosphoric acid,
di-pentafluoropbenyldithioperoxydi- phosphori c acid,
dibenzyldithioperoxydiphosphoric acid,
dicyclohexyldithioperoxydiphosphoric acid, and
dinorbornyldithioperoxydip- hosphoric acid.
[0449] S Valence Stabilizer #25: Examples of
dithioimidodiphosphonic acids, dithiohydrazidodiphosphonic acids,
bis(dithioimidodiphosphonic acids), bis(dithiohydrazidodipbosphonic
acids), poly(dithioimidodiphospho- nic acids),
poly(dithiohydrazidodiphosphonic acids), and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithioimidodiphosphonic acid, methyldithioimidodiphosphonic acid,
isopropyldithioimidodiphosphonic acid,
tert-butyldithioimidodiphospbonic acid,
phenyldithioimidodiphosphonic acid,
pentafluorophenyldithioimidodip- hosphonic acid,
benzyldithioimidodiphosphonic acid,
cyclohexyldithioimidodiphosphonic acid,
norbornyldithioimidodiphosphonic acid,
dimethyldithioimidodiphosphonic acid,
diisopropyldiothioimidodiphos- phonic acid,
di-tert-butyldithioimidodiphosphonic acid,
diphenyldithioimidodipbosphonic acid,
di-pentafluorophenyldithioimidodiph- osphonic acid,
dibenzyldithioimidodiphosphonic acid,
dicyclohexyldithioimidodiphosphonic acid, and
dinorbornyldithioimidodipho- sphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0450] S Valence Stabilizer #26: Examples of
dithioimidodiphosphonamides, dithiohydrazidodiphosphonamides,
bis(dithioimidodiphosphonamides),
bis(dithiohydrazidodiphosphonamides),
poly(dithioimidodiphosphonamides), and
poly(dithiohydrazidodiphosphonamides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: dithioimidodiphosphonamide,
N-methyldithioimidodiphosphonamide, N-isopropyl
dithioimidodiphosphonamid- e,
N-tert-butyldithioimidodiphosphonamide,
N-phenyldithioimidodiphosphonam- ide,
N-pentafluorophenyldithioimidodiphosphonamide,
N-benzyldithioimidodiphosphonamide,
N-cyclohexyldithioimidodiphosphonamid- e,
N-norbornyldithioimidodiphosphonamide,
N,N'"-dimethyldithioimidodiphosp- honamide,
N,N'"-diisopropyldithioimidodiphosphonamide,
N,N'"-di-tert-butyldithioimidodiphosphonamide,
N,N'"-diphenyldithioimidod- iphosphonamide,
N,N'"-di-pentafluorophenyldithioimidodiphosphonamide,
N,N'"-dibenzyldithioimidodiphosphonamide,
N,N'"-dicyclohexyldithioimidodi- phosphonamide, and
N,N'"-dinorbornyldithioimidodiphosphonamide. [Note: The phosphite
(p+3) valence of the phosphorus atom makes stabilizization of high
valence metal ions much more difficult, though still possible.]
[0451] S Valence Stabilizer #27: Examples of
dithiodiphosphonamides, bis(dithiodiphosphonamides), and
poly(dithiodiphosphonamides) (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meetthe requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiodiphosphonamide,
N-methyldithiodiphosphonamide, N-isopropyldithiodiphosphonamide,
N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide,
N-pentafluorophenyldithiodiphosphonamide,
N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide,
N-norbornyldithiodiphosphonamide,
N,N'"-dimethyldithiodiphosphonamide,
N,N'"-diisopropyldithiodiphosphonami- de,
N,N'"-di-tert-butyldithiodiphosphonamidc,
N,N'"-diphenyldithiodiphosph- onamide,
N,N'"-di-pentafluorophenyldithiodiphosphonamide,
N,N'"-dibenzyldithiodiphosphonamide,
N,N'"-dicyclohexyldithiodiphosphonam- ide, and
N,N'"-dinorbornyldithiodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0452] S Valence Stabilizer #28: Examples of dithiodiphosphonic
acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic
acids), and derivatives thereof (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiodiphosphonic acid,
methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid,
tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid,
pentafluorophenyldithiodiphosphonic acid, benzyldithiodiphosphonic
acid, cyclohexyldithiodiphosphonic acid,
norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid,
diisopropyldiothiodiphosphonic acid,
di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic
acid, di-pentafluorophenyldithiodiphosph- onic acid,
dib,enzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphoni- c
acid, and dinorbornyldithiodiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0453] S Valence Stabilizer #29: Examples of
dithioperoxydiphosphonamides, bis(dithioperoxydiphosphonamides),
and poly(dithioperoxydiphosphonamides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: dithioperoxydiphosphona- mide,
N-methyldithioperoxydiphosphonamide,
N-isopropyldithioperoxydiphosph- onamide,
N-tert-butyldithioperoxydiphosphonamide, N-phenyldithioperoxydiph-
osphonamide, N-pentafluorophenyldithioperoxydiphosphonamide,
N-benzyldithioperoxydiphosphonamide,
N-cyclohexyldithioperoxydiphosphonam- ide,
N-norbornyldithioperoxydiphosphonamide,
N,N'"-dimethyldithioperoxydip- hosphonamide,
N,N'"-diisopropyldithioperoxydiphosphonamide,
N,N'"-di-tert-butyldithioperoxydiphosphonamide,
N,N'"-diphenyldithioperox- ydiphosphonamide,
N,N'"-di-pentafluorophenyldithioperoxydiphosphonamide,
N,N'"-dibenzyldithioperoxydiphosphonamide,
N,N'"-dicyclohexyldithioperoxy- diphosphonamide, and
N,N'"-dinorbornyldithioperoxydiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0454] S Valence Stabilizer #30: Examples of
dithioperoxydiphosphonic acids, bis(dithioperoxydiphosphonic
acids), poly(dithioperoxydiphosphonic acids), and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: dithioperoxydiphosphonic acid,
methyldithioperoxydiphosphonic acid,
isopropyldithioperoxydiphosphonic acid,
tert-butyldithioperoxydipho- sphonic acid,
phenyldithioperoxydiphosphonic acid, pentafluorophenyldithio-
peroxydiphosphonic acid, benzyldithioperoxydiphosphonic acid,
cyclohexyldithioperoxydiphosphonic acid,
norbornyldithioperoxydiphosphoni- c acid,
dimethyldithioperoxydiphosphonic acid, diisopropyldithioperoxydiph-
osphonic acid, di-tert-butyldithioperoxydiphosphonic acid,
diphenyldithioperoxydiphosphonic acid,
di-pentafluorophenyldithioperoxydi- phosphonic acid,
dibenzyldithioperoxydiphosphonic acid,
dicyclohexyldithioperoxydiphosphonic acid, and
dinorbornyldithioperoxydip- hosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0455] S Valence Stabilizer #31: Examples of dithiophosphonic acids
(phosphonodithioic acids), bis(dithiophosphonic acids),
poly(dithiophosphonic acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithiophosphonic acid, O-phenyldithiophosphonic acid,
O-benzyldithiophosphonic acid, O-cyclohexyldithiophosphonic acid,
O-norbornyldithiophosphonic acid, O,P-diphenyldithiophosphonic
acid, O,P-dibenzyldithiophosphonic acid,
O,P-dicyclohexyldithiophosphonic acid, and
O,P-dinorbornyldithiophosphoni- c acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0456] S Valence Stabilizer #32: Examples of trithiophosphonic
acids (phosphonotrithioic acids), bis(trithiophosphonic acids),
poly(trithiophosphonic acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trithiophosphonic acid, S-phenyltrithiophosphonic acid,
S-benzyltrithiophosphonic acid, S-cyclohexyltrithiophosphonic acid,
S-norbornyltrithiophosphonic acid, S,P-diphenyltrithiophosphonic
acid, S,P-dibenzyltrithiophosphonic acid,
S,P-dicyclohexyltrithiophosphonic acid, and
S,P-dinorbornyltrithiophospho- nic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #33: Examples of
phosphono(dithioperoxo)thioic acids,
bis[phosphono(dithioperoxo)thioic acids],
poly[phosphono(dithioperoxo)thioic acids], and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphono(dithioperoxo)thioic acid,
O-phenylphosphono(dithioperoxo)thioic acid,
O-benzylphosphono(dithioperoxo)thioic acid,
O-cyclohexylphosphono(d- ithioperoxo)thioic acid,
O-norbornylphosphono(dithioperoxo)thioic acid,
O,P-diphenylphosphono(dithioperoxo)thioic acid,
O,P-dibenzylphosphono(dit- hioperoxo)thioic acid,
O,P-dicyclohexylphosphono(dithioperoxo)thioic acid, and
O,P-dinorbornylphosphono(dithioperoxo)thioic acid. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.]
[0457] S Valence Stabilizer #34: Examples of
phosphono(dithioperoxo)dithio- ic acids,
bis[phosphono(dithioperoxo)dithioic acids],
poly[phosphono(dithioperoxo)dithioic acids], and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: phosphono(dithioperoxo)- dithioic acid,
S-phenylphosphono(dithioperoxo)dithioic acid,
S-benzylphosphono(dithioperoxo)dithioic acid,
S-cyclohexylphosphono(dithi- operoxo)dithioic acid,
S-norbornylphosphono(dithioperoxo)dithioic acid,
S,P-diphenylphosphono(dithioperoxo)dithioic acid,
S,P-dibenzylphosphono(d- ithioperoxo)dithioic acid,
S,P-dicyclohexylphosphono(dithioperoxo)dithioic acid, and
S,P-dinorbornylphosphono(dithioperoxo)dithioic acid. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.]
[0458] S Valence Stabilizer #35: Examples of
S-(alkylthio)thiocarboxylic acids, S-(arylthio)thiocarboxylic
acids, and S,S-thiobisthiocarboxylic Acids (S--S Bidentates and
S--S Tridentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: (methylthio)thioacetic acid;
(methylthio)thiobenzoic acid; (methylthio)thionicotinic acid;
(methylthio)thionapthoic acid; (phenylthio)thioacetic acid;
(phenylthio)thiobenzoic acid; (phenylthio)thionaphthoic acid;
(norbornylthio)thioacetic acid; (norbornylthio)thiobenzoic acid;
(norbornylthio)thionapthoic acid; thiobisthioacetic acid;
thiobisthiobenzoic acid; and thiobisthionapthoic acid.
[0459] S Valence Stabilizer #36: Examples of
S-(alkyldisulfido)thiocarboxy- lic acids,
S-(aryldisulfido)thiocarboxylic acids, and
S,S'-disulfidobisthiocarboxylic acids (S--S Bidentates and S--S
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: (methyldisulfido)thioacetic acid;
(methyldisulfido)thiobenzoic acid; (methyldisulfido)thionicotinic
acid; (methyldisulfido)thionapthoic acid;
(phenyldisulfido)thioacetic acid; (phenyldisulfido)thiobenzoic
acid; (phenyldisulfido)thionaphthoic acid;
(norbornyldisulfido)thioacetic acid;
(norbornyldisulfido)thiobenzoic acid;
(norbornyldisulfido)thionapthoic acid; S,S'-disulfidobisthioacetic
pacid; S,S'-disulfidobisthiobenzoic acid; and
S,S'-disulfidobisthionapthoic acid.
[0460] S Valence Stabilizer #37: Examples of 1,2-dithiolates,
bis(1,2-dithiolates), and poly(1,2-dithiolates) (S--S Bidentates,
S--S Tridentates, S--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2,3-butanedithiol;
1,2-diphenyl-1,2-ethanedithiol- ;
1,2-di(pentafluorophenyl)-1,2-ethanedithio;
1,2-dicyclohexyl-1,2-ethaned- ithiol;
1,2-dinorbornyl-1,2-ethanedithiol; 2,3-dimercaptopropanol;
2,3-dimercaptosuccinic acid; poly[bis(arylthio)acetylene]s; and
poly[bis(alkylylthio)acetylene]s.
[0461] S Valence Stabilizer #38: Examples of rhodanines and
bis(rhodanines) (S--S Bidentates and S--S Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
3-methylrhodanine; 3-ethylrhodanine; 3-isopropylrhodanine;
3-phenylrhodanine; 3-benzylrhodanine; 3-cyclohexylrhodanine;
3-norbornylrhodanine; 5-methylrhodanine; 5-ethylrhodanine;
5-isopropylrhodanine; 5-phenylrhodanine; 5-benzylrhodanine;
5-cyclohexylrhodanine; 5-norbornylrhodanine;
3,3'-ethylenebisrhodanine; 3,3'-propylenerhodanine;
3,3'-butylenerhodanine; 5,5'-ethylenebisrhodanine;
5,5'-propylenerhodanine; and 5,5'-butylenerhodanine. [Note:
rhodanines and bis(rhodanines) tend to stabilize lower oxidation
states in metal ions.]
[0462] S Valence Stabilizer #39: Examples of dithiocarbimates,
bis(dithiocarbimates), and poly(dithiocarbimates) (S--S Bidentates,
S--S Tridentates, and S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
methyldithiocarbimate; trifluoromethyldithiocarbimate;
ethyldithiocarbimate; propyldithiocarbimate;
isopropyldithiocarbimate; butyldithiocarbimate;
tertbutyldithiocarbimate; cyanodithiocarbimate (CDC);
cyanamidodithiocarbimate; azidodithiocarbimate;
phenyldithiocarbimate; pentafluorophenyldithiocarbimate;
benzyldithiocarbimate; naphthyldithiocarbimate;
cyclohexyldithiocarbimate; norbornyldithiocarbimate; and
adamantyldithiocarbimate. [Note: Carbimates tend to stabilize lower
oxidation states in metal ions.]
[0463] S Valence Stabilizer #40: Examples of thioxanthates,
bis(thioxanthates), and poly(thioxanthates) (S--S Bidentates and
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: methyl thioxanthate (MeSxan); ethyl
thioxanthate (EtSxan); isopropyl thioxanthate (iPrSxan);
trifluoromethyl thioxanthate (CF.sub.3Sxan); cyanothioxanthate;
cyanamidothioxanthate; phenyl thioxanthate (PhSxan); benzyl
thioxanthate (BzSxan); pentafluorophenyl thioxanthate; cyclohexyl
thioxanthate (cHxSxan); and norbornyl thioxanthate. [Note:
Thioxanthates tend to stabilize lower oxidation states in metal
ions.]
[0464] S Valence Stabilizer #41: Examples of xanthates,
bis(xanthates), and poly(xanthates) (S--S Bidentates and S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: methyl xanthate (Mexan); ethyl xanthate (Etxan);
isopropyl xanthate (iPrxan); trifluoromethyl xanthate
(CF.sub.3xan); cyanoxanthate; cyanamidoxanthate; phenyl xanthate
(Phxan); benzyl xanthate (Bzxan); pentafluorophenyl xanthate;
cyclohexyl xanthate (cHxxan); and norbornyl xanthate. [Note:
Xanthates tend to stabilize lower oxidation states in metal
ions.]
[0465] S Valence Stabilizer #42: Examples of
phosphinodithioformates (S--S Bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trimethylphosphinodithioformate; triethylphosphinodithioformate;
triphenylphosphinodithioformate;
tricyclohexylphosphinodithioformate;
dimethylphosphinodithioformate; diethylphosphinodithioformate;
diphenylphosphinodithioformate; and
dicyclohexylphosphinodithioformate.
[0466] S Valence Stabilizer #43: Examples of alkyl- and
aryl-dithioborates, trithioborates, perthioborates,
bis(dithioborates), bis(trithioborates), and bis(perthioborates)
(S--S Bidentates and S--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: S,O-diethyl
dithioborate; S,O-diisopropyl dithioborate; S,O-diphenyl
dithioborate; S,O-dibenzyl dithioborate; S,O-dicyclohexyl
dithioborate; S,O-dinorbornyl dithioborate; diethyl trithioborate;
diisopropyl trithioborate; diphenyl trithioborate; dibenzyl
trithioborate; dicyclohexyl trithioborate; and dinorbornyl
trithioborate.
[0467] S Valence Stabilizer #44: Examples of alkyl- and
aryl-dithioboronates and bis(dithioboronates) (S--S Bidentates and
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: diethyl dithioboronate; diisopropyl
dithioboronate; diphenyl dithioboronate; dibenzyl dithioboronate;
dicyclohexyl dithioboronate; and dinorbornyl dithioboronate. [Note:
boronates tend to stabilize lower oxidation states in metal
ions.]
[0468] S Valence Stabilizer #45: Examples of trithioarsonic acids
(arsonotrithioic acids), dithioarsonic acids (arsonodithioic
acids), tetrathioarsonic acids (arsonotetrathioic acids), and
derivatives thereof (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: trithioarsonic acid, O-phenyltrithioarsonic acid,
O-benzyltrithioarsonic acid, O-cyclohexyltrithioarsonic acid,
O-norbornyltrithioarsonic acid, O,S-diphenyltrithioarsonic acid,
O,S-dibenzyltrithioarsonic acid, O,S-dicyclohexyltrithioarsonic
acid, O,S-dinorbornyltrithioarsonic acid; dithioarsonic acid,
O-phenyldithioarsonic acid, O-benzyldithioarsonic acid,
O-cyclohexyldithioarsonic acid, O-norbornyldithioarsonic acid,
O,O-diphenyldithioarsonic acid, O,O-dibenzyldithioarsonic acid,
O,O-dicyclohexyldithioarsonic acid, and
O,O-dinorbornyldithioarsonic acid.
[0469] S Valence Stabilizer #46: Examples of trithioantimonic acids
(stibonotrithioic acids), dithioantimonic acids (stibonodithioic
acids), tetrathioantimonic acids (stibonotetrathioic acids), and
derivatives thereof (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+ include, but are
not limited to: trimethyltrithioantimonate;
triethyltrithioantimonate; and triphenyltrithioantimonate.
[0470] S Valence Stabilizer #47: Examples of phosphine P-sulfides
and amino-substituted phosphine sulfides (S Monodentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trimethylphosphine sulfide (TMPS); triethylphosphine sulfide
(TEPS); triphenylphosphine sulfide (TPhPS); tribenzylphosphine
sulfide (TBzPS); tricyclohexylphosphine sulfide (TcHxPS); and
trinorbornylphosphine sulfide for phosphine P-sulfides; and
tris(dimethylamino)phosphine sulfide; trimorpholinophosphine
sulfide; tripiperidinophosphine sulfide; tripyrrolidinophosphine
sulfide; and tri(cyclohexylamino)phosphine sulfide for
amino-substituted phosphine sulfides.
[0471] S Valence Stabilizer #48: Examples of arsine As-sulfides and
amino-substituted arsine sulfides (S Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trimethylarsine sulfide; triethylarsine sulfide; triphenylarsine
sulfide; tribenzylarsine sulfide; tricyclohexylarsine sulfide; and
trinorbornylarsine sulfide for arsine As-sulfides; and
tris(dimethylamino)arsine sulfide; trimorpholinoarsine sulfide;
tripiperidinoarsine sulfide; tripyrrolidinoarsine sulfide; and
tri(cyclohexylamino)arsine sulfide for amino-substituted arsine
sulfides.
[0472] S Valence Stabilizer #49: Examples of thiolates that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiophenol; naphthalenethiol; 1-dodecanethion; hexadecyl mercaptan;
benzenethiol (bt); polybenzenethiols; and polythioarylenes.
[0473] S Valence Stabilizer #50: Examples of sulfide that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
sulfides (--S.sup.2-); disulfides (--S.sub.2.sup.2-); and
polysulfides (--S.sub.x.sup.2-).
[0474] P Valence Stabilizer #1: Examples of monophosphines (P
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphine, phenylphosphine, diphenylphosphine,
triphenylphosphine, tricyclohexylphosphine,
phenyldimethylphosphine, phenyldiethylphosphine,
methyldiphenylphosphine, ethyldiphenylphosphine, phosphirane,
phosphetane, phospholane, phosphorinane, benzophospholane,
benzophosphorinane, dibenzophospholane, dibenzophosphorinane,
naphthophospholane, naphthophosphorinane, phosphinonorbornane, and
phosphinoadamantane.
[0475] P Valence Stabilizer #2: Examples of diphosphines (P
monodentates or P--P bidentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: diphospholane, benzodiphospholane,
naphthodiphospholane, diphosphorinane, benzodiphosphorinane,
dibenzodiphosphorinane, naphthodiphosphorinane,
bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane,
bis(diphenylphosphino)propane, bis(diphenylphosphino)butane,
bis(diphenylphosphino)pentane, 1,2-bis(dipbenylphosphino)ethylene,
and o-phenylenebis(diphenylphosphine)- . (Note: the aryl
derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.)
[0476] P Valence Stabilizer #3: Examples of triphosphines (P
monodentates, P--P bidentates, or P--P tridentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
triphosphorinane,
P,P'-tetraphenyl-2-methyl-2-(P-diphenyl)phosphinomethyl-1,3-propanediphos-
phine; P,P-[2-(P-diphenyl)phosphinoethyl]diethyl-P-phenylphosphine;
P,P-[2-(P-diphenyl)phosphino]diphenyl-P-phenylphosphine; and
hexahydro-2,4,6-trimethyl-1,3,5-triphosphazine. (Note: the aryl
derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.)
[0477] P Valence Stabilizer #4: Examples of tetraphosphines (P
monodentates, P--P bidentates, P--P tridentates, and P--P
tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to:
P,P'-tetraphenyl-2,2-[(P-diphenyl)phosphinomethyl]-1,3-propanediphosphine-
; tri[o-(P-diphenyl)phosphinophenyl]phosphine; and
1,1,4,7,10,10-hexapheny- l-1,4,7,10-tetraphosphadecane. (Note: the
aryl derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.)
[0478] P Valence Stabilizer #5: Examples of pentaphosphines (P
monodentates, P--P bidentates, P--P tridentates, and P--P
tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to:
4-[2-(P-diphenyl)phosphinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraph-
osphadecane. (Note: the aryl derivatives are air-stable, whereas
the alkyl derivatives are air-sensitive and therefore unsuitable
for these applications.)
[0479] P Valence Stabilizer #6: Examples of hexaphosphines (P--P
bidentates, P--P tridentates, P--P tetradentates, and P--P
hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to:
1,1,10,10-tetraphenyl-4,7-[2-(P,P-diphenyl)phosphinoethyl]-1,4,7,10-tetra-
phosphadecane. (Note: the aryl derivatives are air-stable, whereas
the alkyl derivatives are air-sensitive and therefore unsuitable
for these applications.)
[0480] P Valence Stabilizer #7a: Examples of 5-membered
heterocyclic rings containing one phosphorus atom (P monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: 1-phospholene, 2-phospholene, 3-phospholene, phosphole,
oxaphosphole, thiaphosphole, benzophospholene, benzophosphole,
benzoxaphosphole, benzothiaphosphole, dibenzophospholene,
dibenzophosphole, naphthophospholene, naphthophosphole,
naphthoxaphosphole, naphthothiaphosphole.
[0481] P Valence Stabilizer #7b: Examples of 5-membered
heterocyclic rings containing two phosphorus atoms (P monodentates
or P--P bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: diphospholene, diphosphole,
oxadiphospholene, thiadiphospholene, benzodiphospholene,
benzodiphosphole, naphthodiphospholene, and naphthodiphosphole.
[0482] P Valence Stabilizer #7c: Examples of 5-membered
heterocyclic rings containing three phosphorus atoms (P
monodentates or P--P bidentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: triphosphole.
[0483] P Valence Stabilizer #8a: Examples of 6-membered
heterocyclic rings containing one phosphorus atom (P monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: phosphorin, oxaphosphorin, thiaphosphorin,
benzophosphorin, benzoxaphosphorin, benzothiaphosphorin,
acridophosphine, phosphanthridine, dibenzoxaphosphorin,
dibenzothiaphosphorin, naphthophosphorin, naphthoxaphosphorin, and
naphthothiaphosphorin.
[0484] P Valence Stabilizer #8b: Examples of 6-membered
heterocyclic rings containing two phosphorus atoms (P monodentates
or P--P bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: o-diphosphorin, m-diphosphorin,
p-diphosphorin, oxadiphosphorin, thiadiphosphorin,
benzodiphosphorin, benzoxadiphosphorin, benzothiadiphosphorin,
dibenzodiphosphorin, dibenzoxadiphosphorin,
dibenzothiadiphosphorin, naphthodiphosphorin,
naphthoxadiphosphorin, and naphthothiadiphosphorin.
[0485] P Valence Stabilizer #8c: Examples of 6-membered
heterocyclic rings containing three phosphorus atoms (P
monodentates or P--P bidentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: 1,3,5-triphosphorin,
1,2,3-triphosphorin, benzo-1,2,3-triphosphorin, and
naphtho-1,2,3-triphosphorin.
[0486] P Valence Stabilizer #9a: Examples of 5-membered
heterocyclic rings containing one phosphorus atom and having at
least one additional phosphorus atom binding site not contained in
a ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(P-phenylphosphino)-1-phospholene;
2,5-(P-phenylphosphino)-phosphol- ene;
2-(P-phenylphosphino)-3-phospholene;
2,5-(P-phenylphosphino)-3-phosph- olene;
2-(P-phenylphosphino)phosphole; 2,5-(P-phenylphosphino)phosphole;
2-(P-phenylphosphino)benzophosphole;
7-(P-phenylphosphino)benzophosphole; and
1,8-(P-phenylphosphino)dibenzophosphole.
[0487] P Valence Stabilizer #9b: Examples of 5-membered
heterocyclic rings containing two phosphorus atoms and having at
least one additional phosphorus atom binding site not contained in
a ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(P-phenylphosphino)-1,3-diphospholene;
2,5-(P-phenylphosphino)-1,3-- diphospholene;
2-(P-phenylphosphino)-1,3-diphosphole;
2,5-(P-phenylphosphino)-1,3-diphosphole;
2-(P-phenylphosphino)benzodiphos- phole; and
7-(P-phenylphosphino)benzodiphosphole.
[0488] P Valence Stabilizer #9c: Examples of 5-membered
heterocyclic rings containing three phosphorus atoms and having at
least one additional phosphorus atom binding site not contained in
a ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(P-phenylphosphino)-1,3,4-triphosphole; and
2,5-(P-phenylphosphino)- -1,3,4-triphosphole.
[0489] P Valence Stabilizer #10a: Examples of 6-membered
heterocyclic rings containing one phosphorus atom and having at
least one additional phosphorus atom binding site not contained in
a ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(P-phenylphosphino)phosphorin; 2,5-(P-phenylphosphino)phosphorin;
2-(P-phenylphosphino)benzophosphorin;
7-(P-phenylphosphino)benzophosphori- n; and
1,9-(P-phenylphosphino)acridophosphine.
[0490] P Valence Stabilizer #10b: Examples of 6-membered
heterocyclic rings containing two phosphorus atoms and having at
least one additional phosphorus atom binding site not contained in
a ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(P-phenylphosphino)-4-diphosphorin;
2,6-(P-phenylphosphino)-4-dipho- sphorin;
2,3,5,6-(P-phenylphosphino)-4-diphosphorin;
2-(P-phenylphosphino)benzo-1,4-diphosphorin;
2,3-(P-phenylphosphino)benzo- -1,4-diphosphorin;
2,8-(P-phenylphosphino)benzo-1,4-diphosphorin;
2,3,5,8-(P-phenylphosphino)benzo-1,4-diphosphorin;
1,9-(P-phenylphosphino)dibenzodiphosphorin; and
1,4,6,9-(P-phenylphosphin- o)dibenzodiphosphorin.
[0491] P Valence Stabilizer #10c: Examples of 6-membered
heterocyclic rings containing three phosphorus atoms and having at
least one additional phosphorus atom binding site not contained in
a ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(P-phenylphosphino)-1,3,5-triphosphorin;
2,6-(P-phenylphosphino)-1,3,5-triphosphorin;
4-(P-phenylphosphino)-1,2,3-- triphosphorin; and
8-(P-phenylphosphino)benzo-1,2,3-triphosphorin.
[0492] P Valence Stabilizer #11a: Examples of 5-membered
heterocyclic rings containing one phosphorus atom and having at
least one additional phosphorus atom binding site contained in a
ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1-phospholene; 2,2',2"-tri-1-phospholene;
2,2'-bi-3-phospholene; 2,2', 2"-tri-3-phospholene;
2,2'-biphosphole; 2,2',2"-triphosphole; and
2,2'-bibenzophosphole.
[0493] P Valence Stabilizer #11b: Examples of 5-membered
heterocyclic rings containing two phosphorus atoms and having at
least one additional phosphorus atom binding site contained in a
ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1,3-diphosphole- ne;
2,2'-bi-1,3-diphosphole; and 2,2'-bibenzo-1,3-diphosphole.
[0494] P Valence Stabilizer #11c: Examples of 5-membered
heterocyclic rings containing three phosphorus atoms and having at
least one additional phosphorus atom binding site contained in a
ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1,3,4-triphosphole; and
2,2',2"-tri-1,3,4-triphosphole.
[0495] P Valence Stabilizer #12a: Examples of 6-membered
heterocyclic rings containing one phosphorus atom and having at
least one additional phosphorus atom binding site contained in a
ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-biphosphorin; 2,2',2"-triphosphorin;
2,2',2",2'"-tetraphosphorin; 2,2'-bibenzophosphorin; and
8,8'-bibenzophosphorin.
[0496] P Valence Stabilizer #12b: Examples of 6-membered
heterocyclic rings containing two phosphorus atoms and having at
least one additional phosphorus atom binding site contained in a
ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 3,3'-bi-1,2-diphosphori- n;
3,3',3"-tri-1,2-diphosphorin; 2,2'-bi-1,4-diphosphorin;
2,2',2"-tri-1,4-diphosphorin; 3,3'-bibenzo-1,2-diphosphorin;
8,8'-bibenzo-1,2-diphosphorin; 2,2'-bibenzo-1,4-diphosphorin; and
8,8'-bibenzo-1,4-diphosphorin.
[0497] P Valence Stabilizer #12c: Examples of 6-membered
heterocyclic rings containing three phosphorus atoms and having at
least one additional phosphorus atom binding site contained in a
ring (P Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-1,3,5-triphosphorin;
2,2',2"-tri-1,3,5-triphosphorin; 4,4'-bi-1,2,3-triphosphorin;
4,4'-bibenzo-1,2,3-triphosphorin; and
8,8'-bibenzo-1,2,3-triphosphorin.
[0498] P Valence Stabilizer #13a: Examples of two-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein both
binding sites are composed of phosphorus and are not contained in
component heterocyclic rings (P--P Bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
P,P-diphenyldiphosphacyclobutane ([4]aneP.sub.2);
P,P-diphenyldiphosphacyclopentane ([5]aneP.sub.2);
P,P-diphenyldiphosphacyclohexane ([6]aneP.sub.2);
P,P-diphenyldiphosphacy- cloheptane ([7]aneP.sub.2);
P,P-diphenyldiphosphacyclooctane ([8]aneP.sub.2);
P,P-diphenyldiphosphacyclobutene ([4]eneP.sub.2);
P,P-diphenyldiphosphacyclopentene ([5]eneP.sub.2);
P,P-diphenyldiphosphacyclohexene ([6]eneP.sub.2);
P,P-diphenyldiphosphacy- cloheptene ([7]eneP.sub.2); and
P,P-diphenyldiphosphacyclooctene ([8]eneP.sub.2).
[0499] P Valence Stabilizer #13b: Examples of three-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of phosphorus and are not contained in
component heterocyclic rings (P--P Tridentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
P,P,P-triphenyltriphosphacyclohexane ([6]aneP.sub.3);
P,P,P-triphenyltriphosphacycloheptane ([7]aneP.sub.3);
P,P,P-triphenyltriphosphacyclooctane ([8]aneP.sub.3);
P,P,P-triphenyltriphosphacyclononane ([9]aneP.sub.3);
P,P,P-triphenyltriphosphacyclodecane ([10]aneP.sub.3);
P,P,P-triphenyltriphosphacycloundecane ([11]aneP.sub.3);
P,P,P-triphenyltriphosphacyclododecane ([12]aneP.sub.3);
P,P,P-triphenyltriphosphacyclohexatriene ([6]trieneP.sub.3);
P,P,P-triphenyltriphosphacycloheptatriene ([7]trieneP.sub.3);
P,P,P-triphenyltriphosphacyclooctatriene ([8]trieneP.sub.3);
P,P,P-triphenyltriphosphacyclononatriene ([9]trieneP.sub.3);
P,P,P-triphenyltriphosphacyclodecatriene ([10]trieneP.sub.3);
P,P,P-triphenyltriphosphacycloundecatriene ([11]trieneP.sub.3); and
P,P,P-triphenyltriphosphacyclododecatriene ([12]trieneP.sub.3).
[0500] P Valence Stabilizer #13c: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of phosphorus and are not contained in
component heterocyclic rings (P--P Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
P,P,P,P-tetraphenyltetraphosphacyclooctane ([8]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclononane ([9]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclodecane ([10]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacycloundecane ([11]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclododecane ([12]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclotridecane ([13]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclotetradecane ([14]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclopentadecane ([15]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclohexadecane ([16]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacycloheptadecane ([17]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclooctadecane ([18]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclononadecane ([19]aneP.sub.4);
and P,P,P,P-tetraphenyltetraphosphacycloeicosane
([20]aneP.sub.4).
[0501] P Valence Stabilizer #13d: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of phosphorus and are not contained in
component heterocyclic rings (P--P Tridentates, or P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: P,P,P,P,P-pentaphenylpentaphosphacyclodecane
([10]aneP.sub.5); P,P,P,P,P-pentaphenylpentaphosphacycloundecane
([11]aneP.sub.5); P,P,P,P,P-pentaphenylpentaphosphacyclododecane
([12]aneP.sub.5); P,P,P,P,P-pentaphenylpentaphosphacyclotridecane
([13]aneP.sub.5); P,P,P,P,P-pentaphenylpentaphosphacyclotetradecane
([14]aneP.sub.5); and
P,P,P,P,P-pentaphenylpentaphosphacyclopentadecane
([15]aneP.sub.5).
[0502] P Valence Stabilizer #13e: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of phosphorus and are not contained in
component heterocyclic rings (P--P--P Tridentates, P--P--P--P
Tetradentates, or P--P--P--P--P--P Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
P,P,P,P,P,P-hexaphenylhexaphosphacyclododecane ([12]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotridecane ([13]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotetradecane ([14]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclopentadecane ([15]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclohexadecane ([16]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacycloheptadecane ([17]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclooctadecane ([18]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclononadecane ([19]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacycloeicosane ([20]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacycloheneicosane ([21]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclodocosane ([22]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotricosane ([23]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotetracosane
([24]aneP.sub.6).
[0503] P Valence Stabilizer #13f: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of phosphorus and are not contained in
component heterocyclic rings (P--P Tridentates, P--P Tetradentates,
or P--P Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: P,P,P,P,P,P,P,P-octaphe-
nyloctaphosphacyclohexadecane ([16]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyl- octaphosphacycloheptadecane
([17]aneP.sub.8); P,P,P,P,P,P,P,P-octaphenyloc-
taphosphacyclooctadecane ([18]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctap- hosphacyclononadecane
([19]aneP.sub.8); P,P,P,P,P,P,P,P-octaphenyloctaphos-
phacycloeicosane ([20]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacy- cloheneicosane
([21]aneP.sub.8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycl-
odocosane ([22]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotric- osane
([23]aneP.sub.8); and
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotetr- acosane
([24]aneP.sub.8).
[0504] P Valence Stabilizer #14a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of phosphorus and are contained in
component 5-membered heterocyclic rings (P--P Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetraphospholenes; tetraphospholes; tetraoxaphospholes;
tetradiphospholenes; tetradiphospholes; and
tetraoxadiphospholes.
[0505] P Valence Stabilizer #14b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of phosphorus and are contained in
component 5-membered heterocyclic rings (P--P Tetradentates and
P--P Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: hexaphospholenes; hexaphospholes;
hexaoxaphospholes; hexadiphospholenes; hexadiphospholes; and
hexaoxadiphospholes.
[0506] P Valence Stabilizer #14c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of phosphorus and are contained in
component 5-membered heterocyclic rings (P--P Tridentates; P--P
Tetradentates; or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: octaphospholenes;
octaphospholes; octaoxaphospholes; octadiphospholenes;
octadiphospholes; and octaoxadiphospholes.
[0507] P Valence Stabilizer #15a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of phosphorus and are contained in
a combination of 5-membered heterocyclic rings and phosphine groups
(P--P Tridentates, P--P Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
diphosphatetraphospholenes; tetraphosphatetraphospholenes;
dipbosphatetraphospholes; tetraphosphatetraphospholes;
diphoshatetradiphospholes; and tetraphosphatetradiphospholes.
[0508] P Valence Stabilizer #15b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of phosphorus and are contained in a
combination of 5-membered heterocyclic rings and phosphine groups
(P--P Tridentates, P--P Tetradentates, and P--P Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diphosphahexaphospholenes; triaphosphahexaphospholenes;
diphosphahexaphospholes; triphosphahexaphospholes;
diphoshahexadiphospholes; and triphosphahexadiphospholes.
[0509] P Valence Stabilizer #15c:--Examples of eight membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of phosphorus and are contained in
a combination of 5-membered heterocyclic rings and phosphine groups
(P--P Tridentates, P--P Tetradentates, and P--P Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diphosphaoctaphospholen- es; tetraphosphaoctaphospholenes;
diphosphaoctaphospholes; tetraphosphaoctaphospholes;
diphoshaoctadiphospholes; and tetraphosphaoctadiphospholes.
[0510] P Valence Stabilizer #16a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of phosphorus and are contained in
component 6-membered heterocyclic rings (P--P Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
cyclotetraphosphorins; cyclotetraaoxaphosphorins;
cyclotetradiphosphorins; and cyclotetraoxadiphosphorins.
[0511] P Valence Stabilizer #16b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of phosphorus and are contained in
component 6-membered heterocyclic rings (P--P Tridentates, P--P
Tetradentates, and P--P Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+ include, but are not limited to: cyclohexaphosphorins;
cyclohexaoxaphosphorins; cyclohexadiphosphorins; and
cyclohexaoxadiphosphorins.
[0512] P Valence Stabilizer #16c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of phosphorus and are contained in
component 6-membered heterocyclic rings (P--P Tridentates, P--P
Tetradentates, and P--P Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: cyclooctaphosphorins;
cyclooctaoxaphosphorins; cyclooctadiphosphorins; and
cyclooctaoxadiphosphorins.
[0513] P Valence Stabilizer #17a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of phosphorus and are contained in
a combination of 6-membered heterocyclic rings and phosphine groups
(P--P Tridentates, P--P Tetradentates, or P--P Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diphosphacyclotetraphosphorins; tetraphosphacyclotetraphosphorins;
diphosphacyclotetraoxaphosphorins;
tetraphosphacyclotetraoxaphosphorins;
diphosphacyclotetradiphosphorins;
tetraphosphacyclotetradiphosphorins;
diphosphacyclotetraoxadiphosphorins; and
tetraphosphacyclotetraoxadiphosphorins.
[0514] P Valence Stabilizer #17b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of phosphorus and are contained in a
combination of 6-membered heterocyclic rings and phosphine groups
(P--P Tridentates, P--P Tetradentates, or P--P Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diphosphacyclohexaphosphorins; triphosphacyclohexaphosphorins;
diphosphacyclohexaoxaphosphorins;
triphosphacyclohexaoxaphosphorins; diphosphacyclohexadiphosphorins;
triphosphacyclohexadiphosphorins;
diphosphacyclohexaoxadiphosphorins; and
triphosphacyclohexaoxadiphosphorins.
[0515] P Valence Stabilizer #17c: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
eight binding sites are composed of phosphorus and are contained in
a combination of 6-membered heterocyclic rings and phosphine groups
(P--P Tridentates, P--P Tetradentates, or P--P Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diphosphacyclooctaphosphorins; tetraphosphacyclooctaphosphorins;
diphosphacyclooctaoxaphosphorins;
tetraphosphacyclooctaoxaphosphorins;
diphosphacyclooctadiphosphorins;
-tetraphosphacyclooctadiphosphorins;
diphosphacyclooctaoxadiphosphorins; and
tetraphospbacyclooctaoxadiphosphorins.
[0516] O Valence Stabilizer #1: Examples of dithioperoxydicarbonic
acids, bis(dithioperoxydicarbonic acids),
poly(dithioperoxydicarbonic acids), and derivatives thereof (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithioperoxydicarbonic acid, O-phenyldithioperoxydicarbonic acid;
O-benzyldithioperoxydicarbonic acid;
O-cyclohexyldithioperoxydicarb- onic acid;
O-norbornyldithioperoxydicarbonic acid; O,O'-diphenyldithiopero-
xydicarbonic acid; O,O'-dibenzyldithioperoxydicarbonic acid;
O,O'-dicyclohexyldithioperoxydicarbonic acid; and
O,O'-dinorbornyldithiop- eroxydicarbonic acid.
[0517] O Valence Stabilizer #2: Examples of imidodiphosphonic
acids, hydrazidodiphosphonic acids, bis(imidodiphosphonic acids),
bis(hydrazidodiphosphonic acids), poly(imidodiphosphonic acids),
poly(hydrazidodiphosphonic acids), and derivatives thereof (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
imidodiphosphonic acid, methylimidodiphosphonic acid,
isopropylimidodiphosphonic acid, tert-butylimidodiphosphonic acid,
phenylimidodiphosphonic acid, pentafluorophenylimidodiphosphonic
acid, benzylimidodiphosphonic acid, cyclohexylimidodiphosphonic
acid, norbornylimidodiphosphonic acid, dimethylimidodiphosphonic
acid, diisopropylimidodiphosphonic acid,
di-tert-butylimidodiphosphonic acid, diphenylimidodiphosphonic
acid, di-pentafluorophenylimidodiphosphonic acid,
dibenzylimidodiphosphonic acid, dicyclohexylimidodiphosphonic acid,
and dinorbornylimidodiphosphoni- c acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0518] O Valence Stabilizer #3: Examples of imidodiphosphonamides,
hydrazidodiphosphonamides, bis(imidodiphosphonamides),
bis(hydrazidodiphosphonamides), poly(imidodiphosphonamides), and
poly(hydrazidodiphosphonamides) (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4include,
but are not limited to imidodiphosphonamide,
N-methylimidodiphosphonamide, N-isopropylimidodiphosphonamide,
N-tert-butylimidodiphosphonamide, N-phenylimidodiphosphonamide,
N-pentafluorophenylimidodiphosphonamide,
N-benzylimidodiphosphonamide, N-cyclohexylimidodiphosphonamide,
N-norbornylimidodiphosphonamide,
N,N'"-dimethylimidodiphosphonamide,
N,N'"-diisopropylimidodiphosphonamide,
N,N'"-di-tert-butylimidodiphosphon- amide,
N,N'"-diphenylimidodiphosphonamide,
N,N'"-di-pentafluorophenylimido- diphosphonamide,
N,N'"-dibenzylimidodiphosphonamide,
N,N'"-dicyclohexylimidodiphosphonamide, and
N,N'"-dinorbornylimidodiphosp- honamide. [Note: The phosphite (p+3)
valence of the phosphorus atom makes stabilizization of high
valence metal ions much more difficult, though still possible.]
[0519] O Valence Stabilizer #4: Examples of diphosphonamides,
bis(diphosphonamides), and poly(diphosphonamides) (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diphosphonamide,
N-methyldiphosphonamide, N-isopropyldiphosphonamide,
N-tert-butyldiphosphonamide, N-phenyldiphosphonamide,
N-pentafluorophenyldiphosphonamide, N-benzyldiphosphonamide,
N-cyclohexyldiphosphonamide, N-norbornyldiphosphonamide,
N,N'"-dimethyldiphosphonamide, N,N'"-diisopropyldiphosphonamide,
N,N'"-di-tert-butyldiphosphonamide, N,N'"-diphenydiphosphonamide,
N,N'"-di-pentafluorophenyldiphosphonamide,
N,N'"-dibenzyldiphosphonamide, N,N'"-dicyclohexyldiphosphonamide,
and N,N"-dinorbornyldiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0520] O Valence Stabilizer #5: Examples of carbonates and
bis(carbonates) (O--O Bidentates and O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
carbonate; bicarbonate; O,O-diethylcarbonate; diisopropylcarbonate;
diphenylcarbonate; dibenzylcarbonate; dicyclohexylcarbonate; and
dinorbornylcarbonate.
[0521] O Valence Stabilizer #6: Examples of carbazates
(carbazides), bis(carbazates), and poly(carbazates)
(O--OBidentates, O-O-Tridentates, and O--O Tetradentates; or
possibly N--O Bidentates, N--O Tridentates, and N--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: N,N'-dimethylcarbazate;
N,N'-di(trifluoromethyl)carbazate- ; N,N'-diethylcarbazate;
N,N'-diphenylcarbazate; N,N'-dibenzylcarbazate;
N,N'-di(pentafluorophenyl)carbazate; N,N'-dicyclohexylcarbazate;
and N,N'-dinorbornylcarbazate.
[0522] O Valence Stabilizer #7: Examples of arsonic acids,
bis(arsonic acids), poly(arsonic acids), and derivatives thereof
(O--O Bidentates, O--O Tridentates, O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to: arsonic
acid, O-phenylarsonic acid, O-benzylarsonic acid,
O-cyclohexylarsonic acid, O-norbornylarsonic acid,
O,O-diphenylarsonic acid, O,O-dibenzylarsonic acid,
O,O-dicyclohexylarsonic acid, O,O-dinorbornylarsonic acid; and
aminophenylarsonic acids.
[0523] O Valence Stabilizer #8: Examples of alkyl- and aryl-borates
and bis(borates) (O--O Bidentates and O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
triethyl borate; diisopropyl borate; diphenyl borate; dibenzyl
borate; dicyclohexyl borate; and dinorbornyl borate.
[0524] O Valence Stabilizer #9: Examples of alkyl- and
aryl-boronates and bis(boronates) (O--O Bidentates and O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: diethyl boronate; diisopropyl boronate; diphenyl
boronate; dibenzyl boronate; dicyclohexyl boronate; and dinorbornyl
boronate. [Note: boronates tend to stabilize lower oxidation states
in metal ions.]
[0525] O Valence Stabilizer #10: Examples of phosphine P-oxides and
amino-substituted phosphine oxides (O Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trimethylphosphine oxide (TMPO); triethylphosphine oxide (TEPO);
triphenylphosphine oxide (TPhPO); tribenzylphosphine oxide (TBzPO);
tricyclohexylphosphine oxide (TcHxPO); and trinorbornylphosphine
oxide for phosphine P-oxides; and hexamethylphosphoramide (HMPA);
trimorpholinophosphine oxide (TMrPO); tripiperidinophosphine oxide;
tripyrrolidinophosphine oxide; and tri(cyclohexylamino)phosphine
oxide for amino-substituted phosphine oxides.
[0526] O Valence Stabilizer #11: Examples of arsine As-oxides and
amino-substituted arsine oxides (O Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trimethylarsine oxide (TMAsO); triethylarsine oxide (TEAsO);
triphenylarsine oxide (TPhAsO); tribenzylarsine oxide (TBzAsO);
tricyclohexylarsine oxide (TcHxAsO); and trinorbornylarsine oxide
for arsine As-oxides; and hexamethylarsonamide; trimorpholinoarsine
oxide; tripiperidinoarsine oxide; tripyrrolidinoarsine oxide; and
tri(cyclohexylamino)arsine oxide for amino-substituted arsine
oxides.
[0527] O Valence Stabilizer #12a: Examples of 5-membered
heterocyclic rings containing one oxygen atom (O monodentate) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
furan, dihydrofuran, oxazole, isoxazole, oxadiazole, oxatriazole,
oxathiole, benzofuran, benzodihydrofuran, benzoxazole,
benzisoxazole, benzoxadiazole (benzofurazan), dibenzofuran,
dibenzoxazole, dibenzisoxazole, naphthofuran, naphthoxazole,
naphthisoxazole, and naphthoxadiazole.
[0528] O Valence Stabilizer #12b: Examples of 5-membered
heterocyclic rings containing two oxygen atoms (O monodentate or
O--O bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dioxolane, benzodioxolane, and
naphthodioxolane.
[0529] O Valence Stabilizer #13a: Examples of 6-membered
heterocyclic rings containing one oxygen atom (O monodentate) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dihydropyran, pyran, oxazine, oxadiazine, oxatriazine, oxathiin,
benzopyran, benzoxazine, benzoxadiazine, dibenzopyran,
naphthopyran, naphthoxazine, and naphthoxadiazine.
[0530] O Valence Stabilizer #13b: Examples of 6-membered
heterocyclic rings containing two oxygen atoms (O monodentate or
O--O bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dihydrodioxane, dioxane, benzodioxane,
dibenzodioxane, and naphthodioxane.
[0531] O Valence Stabilizer #14a: Examples of 5-membered
heterocyclic rings containing one oxygen atom and having at least
one additional oxygen atom binding site not contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,5-dihydroxy-2,5-dihydrofuran;
2,5-bis(hydroxymethyl)-2,5-dihydrofuran;
2,5-bis(2-hydroxyphenyl)-2,5-dihydrofuran; 2,5-dihydroxyfuran;
2,5-bis(hydroxymethyl)furan; and 2,5-bis(2-hydroxyphenyl)furan.
[0532] O Valence Stabilizer #14b: Examples of 5-membered
heterocyclic rings containing two oxygen atoms and having at least
one additional oxygen atom binding site not contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-hydroxy-1,3-dioxolane;
2-hydroxymethyl)-1,3-dioxolane; 4,5-dihydroxy-1,3-dioxolane;
4,5-bis(2-hydroxyphenyl)-1,3-dioxolane; 2-hydroxybenzodioxolane;
and 7-hydroxybenzodioxolane.
[0533] O Valence Stabilizer #15a: Examples of 6-membered
heterocyclic rings containing one oxygen atom and having at least
one additional oxygen atom binding site not contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,6-dihydroxy-2,5-dihydropyran;
2,6-bis(hydroxymethyl)-2,5-dihydropyran;
2,6-bis(2-hydroxyphenyl)-2,5-dihydropyran; 2,6-dihydroxypyran;
2,6-bis(hydroxymethyl)pyran; 2,6-bis(2-hydroxyphenyl)pyran;
2-hydroxy-1-benzopyran; 8-hydroxy-1-benzopyran; and
1,9-dihydroxydibenzopyran.
[0534] O Valence Stabilizer #15b: Examples of 6-membered
heterocyclic rings containing two oxygen atoms and having at least
one additional oxygen atom binding site not contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band".valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-hydroxy-1,4-dioxane;
2,6-dihydroxy-1,4-dioxane; 2,6-bis(2-hydroxyphenyl- )-1,4-dioxane;
2,3-dihydroxy-1,4-benzodioxane; 5,8-dihydroxy-1,4-benzodiox- ane;
1,8-dihydroxydibenzodioxane; and
1,4,5,8-tetrahydroxydibenzodioxane.
[0535] O Valence Stabilizer #16a: Examples of 5-membered
heterocyclic rings containing one oxygen atom and having at least
one additional oxygen atom binding site contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,2'-bi-2,5-dihydrofuran; 2,2',2"-tri-2,5-dihydrofuran;
2,2'-bifuran; 2,2',2"-trifuran; 1,1'-bis(dibenzofuran); and
polyfurans.
[0536] O Valence Stabilizer #16b: Examples of 5-membered
heterocyclic rings containing two oxygen atoms and having at least
one additional oxygen atom binding site contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2,2'-bi-1,3-dioxolane;
4,4'-bi-1,3-dioxolane; 7,7'-bi-1,2-benzodioxolane; and
3,3'-bi-1,2-benzodioxolane.
[0537] O Valence Stabilizer #17a: Examples of 6-membered
heterocyclic rings containing one oxygen atom and having at least
one additional oxygen atom binding site contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,2'-bi-2,5-dihydropyran; 2,2',2"-tri-2,5-dihydropyran;
2,2'-bipyran; 2,2',2"-tripyran; and 1,1'-bis(dibenzopyran).
[0538] O Valence Stabilizer #17b: Examples of 6-membered
heterocyclic rings containing one oxygen atom and having at least
one additional oxygen atom binding site contained in a ring (O
monodentates, O--O bidentates, O--O tridentates, O--O
tetradentates, or O--O hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2,2'-bi-1,4-dioxane;
2,2'-bi-1,3-dioxane; 5,5'-bi-1,4-benzodioxane; and
2,2'-bi-1,3-benzodioxane.
[0539] O Valence Stabilizer #18a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of oxygen (usually ester or hydroxyl
groups) and are not contained in component heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 8-crown-4; 10-crown-4; 12-crown-4; 14-crown-4;
16-crown-4; 18-crown-4; 20-crown-4; dibenzo-8-crown-4;
dibenzo-10-crown-4; dibenzo-12-crown-4; dibenzo-14-crown-4;
dibenzo-16-crown-4; dibenzo-18-crown-4; dibenzo-20-crown-4;
tetrabenzo-8-crown-4; tetrabenzo-10-crown-4; tetrabenzo-12-crown-4;
tetrabenzo-14-crown-4; tetrabenzo-16-crown-4;
tetrabenzo-18-crown-4; and tetrabenzo-20-crown-4.
[0540] O Valence Stabilizer #18b: Examples of five-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of oxygen (usually ester or hydroxyl
groups) and are not contained in component heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 10-crown-5; 15-crown-5; 20-crown-5; 25-crown-5;
pentabenzo-10-crown-5; pentabenzo-15-crown-5;
pentabenzo-20-crown-5; and pentabenzo-25-crown-5.
[0541] O Valence Stabilizer #18c: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of oxygen (usually ester or hydroxyl
groups) and are not contained in component heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 12-crown-6; 18-crown-6; 24-crown-6; 30-crown-6;
36-crown-6; tribenzo-12-crown-6; tribenzo-18-crown-6;
tribenzo-24-crown-6; tribenzo-30-crown-6; tribenzo-36-crown-6;
hexabenzo-12-crown-6; hexabenzo-18-crown-6; hexabenzo-24-crown-6;
hexabenzo-30-crown-6; and hexabenzo-36-crown-6.
[0542] O Valence Stabilizer #18d: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of oxygen (usually ester or hydroxyl
groups) and are not contained in component heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 14-crown-7; 21-crown-7; 28-crown-7; 35-crown-7;
heptabenzo-14-crown-7; heptabenzo-21-crown-7;
heptabenzo-28-crown-7; and heptabenzo-35-crown-7.
[0543] O Valence Stabilizer #18e: Examples of eight-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of oxygen (usually ester or hydroxyl
groups) and are not contained in component heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 16-crown-8; 24-crown-8; 32-crown-8; 40-crown-8;
48-crown-8; tetrabenzo-16-crown-8; tetrabenzo-24-crown-8;
tetrabenzo-32-crown-8; tetrabenzo-40-crown-8;
tetrabenzo-48-crown-8; octabenzo-16-crown-8; octabenzo-24-crown-8;
octabenzo-32-crown-8; octabenzo-40-crown-8; and
octabenzo-48-crown-8.
[0544] O Valence Stabilizer #18f: Examples of ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of oxygen (usually ester or hydroxyl
groups) and are not contained in component heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 20-crown-10; 30-crown-10; 40-crown-10; 50-crown-10;
pentabenzo-20-crown-10; pentabenzo-30-crown-10;
pentabenzo-40-crown-10; and pentabenzo-50-crown-10.
[0545] O Valence Stabilizer #19: Examples of four-, five-, six-,
seven-, eight-, and ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of oxygen and
are contained in component 5-membered heterocyclic rings (O--O
Bidentates, O-O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tetrafurans, tetrabenzofurans; pentafurans;
pentabenzofurans; hexafurans; hexabenzofurans; heptafurans;
heptabenzofurans; octafurans; octabenzofurans; decafurans; and
decabenzofurans.
[0546] O Valence Stabilizer #20: Examples of four-, five-, six-,
seven-, eight-, and ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of oxygen and
are contained in component 6-membered heterocyclic rings (O--O
Bidentates, O--O Tridentates, O--O Tetradentates, and O--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tetrapyrans, tetrabenzopyrans; pentapyrans;
pentabenzopyans; hexapyans; hexabenzopyans; heptapyans;
heptabenzopyans; octapyans; octabenzopyans; decapyans; and
decabenzopyans.
[0547] N--S Valence Stabilizer #1: Examples of thioimidates,
dithioimidates, polythioimidates, and derivatives of thioimidic
acid (N--S bidentates and N--S tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
S-methyl formathioimidate; S-ethyl formathioimidate; S-methyl
acetathioimidate; S-ethyl acetathioimidate; S-methyl
benzthioimidate; S-ethyl benzthioimidate; S-methyl
cyclohexylthioimidate; S-ethyl cyclohexylthioimidate; S-methyl
pentafluorobenzthioimidate; S-ethyl pentafluorobenzthioimidate;
S-methyl 2-pyridylthioimidate; S-ethyl 2-pyridylthioimidate;
S,S'-dimethyl benzdithioimidate; S,S'-dimethyl
tetrafluorobenzdithioimidate; 2-iminothiolane; and
2-iminotetrahydrothiopyran. [Note: Many thioimidate complexes are
decomposed by water, but their stability can be enhanced through
the use of fluorinated solubility control anions (e.g.
PF.sub.6.sup.-).]
[0548] N--S Valence Stabilizer #2: Examples of thioguanylureas,
guanidinothioureas, bis(thioguanylureas), bis(guanidinothioureas,
pQly(thioguanylureas), and poly(guanidinothioureas) (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: thioguanylurea
(amidinothiourea); guanidinothiourea; methylthioguanylurea;
ethylthioguanylurea; isopropylthioguanylurea; butylthioguanylurea;
benzylthioguanylurea; phenylthioguanylurea; tolylthioguanylurea;
naphthylthioguanylurea; cyclohexylthioguanylurea;
norbornylthioguanylurea; adamantylthioguanylurea;
dimethylthioguanylurea; diethylthioguanylurea;
diisopropylthioguanylurea; dibutylthioguanylurea;
dibenzylthioguanylurea; diphenylthioguanylurea;
ditolylthioguanylurea; dinaphthylthioguanylurea;
dicyclohexylthioguanylurea; dinorbornylthioguanylurea;
diadamantylthioguanylurea; ethylenebis(thioguanylurea);
propylenebis(thioguanylurea); phenylenebis(thioguanylurea);
piperazinebis(thioguanylurea); oxalylbis(thioguanylurea);
malonylbis(thioguanylurea); succinylbis(thioguanylurea); and
phthalylbis(thioguanylurea). [Note: thioguanylureas generally tend
to favor lower oxidation states in complexed metals.]
[0549] N--S Valence Stabilizer #3: Examples of amidinothioamides,
guanidinothioamides, bis(amidinothioamides),
bis(guanidinothioamides), poly(amidinothioamides), and
poly(guanidinothioamides) (including both N-amidinothioamides and
2-amidinothioacetamides) (N--S Bidentates, N--S Tridentates, and
N--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: amidinothioacetamide; guanidinothioamide,
amidinothiopropanamide; amidinothiobutanamide;
amidinothiobenzamide; amidinothiotoluamide;
amidinothiocyclohexamide; N-methylamidinothioacetamide;
N-ethylamidinothiopropanamide; N-propylamidinothiobutanamide;
N-phenylamidinothiobenzamide; N-tolylamidinothiotoluamide;
N-cyclohexylamidinothiocyclohexamide; bis(amidinothiooxamide);
bis(amidinothiomalonamide); bis(amidinothiosuccinamide);
bis(amidinothiophthalamide); 2-amidinothioacetamide
(thiomalonamamidine); N-methyl-2-amidinothioacetam- ide;
N-ethyl-2-amidinothioacetamide; N-phenyl-2-amidinothioacetamide;
N-benzyl-2-amidinothioacetamide;
N-cyclohexyl-2-amidinothioacetamide;
N,N'-dimethyl-2-amidinothioacetamide;
N,N'-diethyl-2-amidinothioacetamide- ;
N,N'-diphenyl-2-amidinothioacetamide;
N,N'-dibenzyl-2-amidinothioacetami- de; and
N,N'-dicyclohexyl-2-amidinothioacetamide. [Note: amidinothioamides
generally tend to favor lower oxidation states in complexed
metals.]
[0550] N--S Valence Stabilizer #4: Examples of imidoylthioamides,
bis(imidoylthioamides), and poly(imidoylthioamides); (N--S
Bidentates, N--S Tridentates, and N--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
acetimidoylthioacetamide; acetimidoylthiopropanamide;
acetimidoylthiobutanamide; acetimidoylthiobenzamide;
acetimidolylthiotoluamide; acetimidoylthiocyclohexamide;
propimidoylthiopropanamide; butimidoylthiobutanamide;
benzimidoylthiobenzamide; ethylenebis(acetimidoylthioacetamide);
propylenebis(acetimidoylthioacetam- ide); and
phenylenebis(acetimidoylthioacetamide). [Note: imidoylthioamides
generally tend to favor lower oxidation states in complexed
metals.]
[0551] N--S Valence Stabilizer #5: Examples of thioureas,
bis(thioureas), and poly(thioureas), including thiourylene
complexes (N--S bidentates and N--S tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiourea; methylthiourea; ethylthiourea; isopropylthiourea;
benzylthiourea; phenylthiourea; cyclohexylthiourea;
naphthylthiourea (ntu); biphenylthiourea; norbornylthiourea;
adamantylthiourea; N,N'-dimethylthiourea; N,N'-diethylthiourea;
N,N'-diisopropylthiourea; N,N'-dibenzylthiourea;
N,N'-dicyclohexylthiourea; N,N'-dinapthylthiourea;
N,N'-dibiphenylthiourea; N,N'-dinorbornylthiourea;
N,N'-diadamantylthiourea; tetramethylthiourea; ethylenethiourea
(2-imidazolidinethione)(etu); 4,5-dihydroxy-2-imidazolinethione
(dhetu); propylenethiourea; N-(thiazol-2-yl)thiourea;
diphenylphosphinothioyl thioureas; allylthiourea;
N-allyl-N'-pyridylthiourea; N-allyl-N'-anisylthiourea;
N-allyl-N'-naphthylthiourea; N-allyl-N'-phenylthiourea;
thioglycoluril (acetylenethiourea); and bis(pyridylmethyl)thiourea.
[Note: thioureas generally tend to favor lower oxidation states in
complexed metals.]
[0552] N--S Valence Stabilizer #6: Examples of thiocarboxamides,
bis(thiocarboxamides), and poly(thiocarboxamides), (N--S
bidentates, N--S tridentates, and N--S tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiocarbamide (tu); thioacetamide (taa); thiopropionamide;
thiobutanamide; thiobenzamide (1-pbenylthioformamide)(t- ba);
1-naphthylthioformamide; 1-cyclohexylthioformamide);
1-norbornylthioformamide; 1-adamantylthioformamide;
N,N-dimethylthioformamide; N,N-dimethylthioacetamide;
pyridine-2-thiocarboxamide (thiopicolinamide);
pyrazine-2,3-dithiocarboxa- mide; thionicotinamide;
2-thiophenethiocarhoxamide; N N-dimethylthiobenzamide;
N-ethylthiocarbamide (N-etu); tetramethylthiocarbamide (tmtu);
2-thioacetamidothiazole (tatz); and polythioacrylamides. [Note:
thiocarboxamides generally tend to favor lower oxidation states in
complexed metals.]
[0553] N--S Valence Stabilizer #7: Examples of imidosulfurous
diamides and bis(imidosulfurous diamides) (N--S Bidentates, N--S
Tridentates, and N--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
N,N'-diphenylimidosulfurous diamide; N,N'-dibenzylimidosulfur- ous
diamide; and phenylenebis(imidosulfurous diamide). [Note: These
complexes tend to hydrolyze unless stabilized with a fluorinated
anionic solubility control agent. The sulfite (S.sup.+4) valence of
the sulfur atom makes stabilizization of high valence metal ions
much more difficult, though still possible.]
[0554] N--S Valence Stabilizer #8: Examples of sulfurdiimines,
bis(sulfurdiimines), and poly(sulfurdiimines) (N--S Bidentates,
N--S Tridentates, and N--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N,N'-diphenylsulfurdiimine; N,N'-dibenzylsulfurdiimine; and
phenylenebis(sulfurdiimine). [Note: These complexes tend to
hydrolyze unless stabilized with a fluorinated anionic solubility
control agent. The sulfite (S.sup.+4) valence of the sulfur atom
makes stabilizization of high valence metal ions much more
difficult, though still possible.]
[0555] N--S Valence Stabilizer #9: Examples of phosphonimidothioic
acid, phosphonimidodithioic acid, bis(phosphonimidothioic acid);
bis(phosphonimidodithioic acid), and derivatives thereof (N--S
Bidentates, N--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: phosphonimidothioic acid,
phosphonimidodithioic acid; O-phenylphosphonimidothioic acid;
O-benzylphosphonimidothioic acid; O-cyclohexylphosphonimidothioic
acid; O-norbornylphosphonimidothioic acid;
S-phenylphosphonimidodithioic acid; S-benzylphosphonimidodithioic
acid; S-cyclohexylphosphonimidodithioic acid; and
S-norbornylphosphonimid- odithioic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0556] N--S Valence Stabilizer #10: Examples of phosphonothioic
diamides, bis(phosphonothioic diamides), and poly(phosphonothioic
diamides) (N--S Bidentates and N--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphonothioic diamide, phosphonothioic dihydrazide,
phosphonamidothioic hydrazide, N-phenylphosphonothioic diamide,
N-benzylphosphonothioic diamide, N-cyclohexylphosphonothioic
diamide, and N-norbornylphosphonothioic diamide. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.]
[0557] N--S Valence Stabilizer #11: Examples of phosphonamidothioic
acid, phosphonamidiinidodithioic acid, bis(phosphonamidothioic
acid), bis(phosphonamidimidodithioic acid),
poly(phosphonamidothioic acid), and poly(phosphonamidimidodithioic
acid), and derivatives thereof (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: phosphonamidothioic acid, phosphonamidimidodithio-
ic acid, phosphonohydrazidodithioic acid, phosphonohydrazidothioic
acid, S-phenylphosphonamidimidodithioic acid,
S-benzylphosphonamidimidodithioic acid,
S-cyclohexylphosphonamidimidodithioic acid, and
S-norbornylphosphonamidimidodithioic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0558] N--S Valence Stabilizer #12: Examples of beta-aminothiones
(N-substituted 3-amino-2-propenethioaldehydes),
bis(beta-aminothiones), and poly(beta-aminothiones) (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
4-methylamino-3-penten-2-thione; 4-ethylamino-3-penten-2-thione;
4-isopropyl amino-3-penten-2-thione;
4-phenylamino-3-penten-2-thione; 4-naphthylamino-3-penten-2-thione;
4-cyclohexylamino-3-penten-2-thione;
4-norbornylamino-3-penten-2-thione;
4-hydroxyamino-3-penten-2-thione;
3-methylamino-1-phenyl-2-butenethioaldehydel;
3-ethylamino-1-phenyl-2-but- enethioaldehyde;
3-isopropylamino-1-phenyl-2-butenethioaldehyde;
3-phenylamino-1-phenyl-2-butenethioaldehyde;
3-naphthylamino-1-phenyl-2-b- utenethioaldehyde;
3-cyclohexylamino-1-phenyl-2-butenethioaldehyde;
3-norbornylamino-1-phenyl-2-butenethioaldehyde;
3-hydroxyamino-1-phenyl-2- -butenethioaldehyde;
3-phenylamino-1,3-diphenyl-2-propenethioaldehyde;
3-cyclohexylamino-1,3-dicyclohexyl-2-propenethioaldehyde; and
3-norbornylamino-1,3-dinorbornyl-2-propenethioaldehyde.
[0559] N--S Valence Stabilizer #13: Examples of
3-aminothioacrylamides (3-amino-2-thiopropenamides),
3,3-diaminothioacrylamides, bis(3-aminothioacrylamides),
bis(3,3-diaminothioacrylamides), poly(3-aminothioacrylamides), and
poly(3,3-diaminothioacrylamides) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 3-methylaminothioacryl amide;
3-ethylaminothioacrylamide, 3-i sopropyl aminothioacryl amide,
3-phenylaminothioacrylamide; 3-naphthylaminothioacrylamide;
3-cyclohexylaminothioacrylamide; 3-norbornylaminothioacrylamide;
3-hydroxyaminothioacrylamide; N--ethyl-3-methylaminothioacrylamide;
N-ethyl-3-ethylaminothioacrylamide,
N-isopropyl-3-isopropylaminothioacryl- amide,
N-phenyl-3-phenylaminothioacrylamide;
N-naphthyl-3-naphthylaminothi- oacrylamide;
N-cyclohexyl-3-cyclohexylaminothioacrylamide;
N-norbornyl-3-norbornylaminothioacrylamide;
3-amino-3-methylaminothioacry- lamide;
3-amino-3-ethylaminothioacrylamide, 3-amino-3-isopropylaminothioac-
rylamide, 3-amino-3-phenylaminothioacrylamide;
3-amino-3-naphthylaminothio- acrylamide;
3-amino-3-cyclohexylaminothioacrylamide;
3-amino-3-norbornylaminothioacrylamide; and
3-amino-3-hydroxyaminothioacr- ylamide.
[0560] N--S Valence Stabilizer #14: Examples of 3-aminothioacrylic
acids (3-amino-2-thiopropenoic acids),
3-mercapto-3-aminothioacrylic acids, bis(3-aminothioacrylic acids),
bis(3-mercapto-3-aminothioacrylic acids), poly(3-aminothioacrylic
acids), and poly(3-mercapto-3-aminothioacrylic acids), and
derivatives thereof (N--S Bidentates and N--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
3-aminothioacrylic acid; 3-mercapto-3-aminothioacrylic acid;
3-methylaminothioacrylic acid; 3-ethylaminothioacrylic acid;
3-isopropylaminothioacrylic acid; 3-phenylaminothioacrylic acid;
3-naphthylaminothioacrylic acid; 3-cyclohexylaminothioacrylic acid;
3-norbornylaminothioacrylic acid; 3-hydroxyaminothioacrylic acid;
methyl 3-methylaminothioacrylate; ethyl 3-ethylaminothioacrylate;
isopropyl 3-isopropylaminothioacrylate; benzyl
3-phenylaminothioacrylate; naphthyl 3-naphthylaminothioacrylate;
cyclohexyl 3-cyclohexylaminothioacrylate; and norbornyl
3-norbornylaminothioacryl ate.
[0561] N--S Valence Stabilizer #15: Examples of N-thioacyl
benzylidenimines, bis(N-thioacyl benzylidenimines), and
poly(N-thioacyl benzylidenimines) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: N-thioformyl benzylidenimine, N-thioacetyl
benzylidenimine; N-thiobenzoyl benzylidenimine; and
N-pentafluorothiobenzoyl benzylidenimine.
[0562] N--S Valence Stabilizer #16: Examples of thiocarbonyl
oximes, bis(thiocarbonyl oximes), and poly(thiocarbonyl oximes)
(N--S Bidentates, N--S Tridentates, and N--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
butane-3-thione-2-one monoxime); and diphenylethane-2-thione-1-one
monoxime.
[0563] N--S Valence Stabilizer #17: Examples of mercapto oximes,
bis(mercapto oximes), and poly(mercapto oximes) (including 2-sulfur
heterocyclic oximes) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 3-mercaptobutan-2-one
oxime; 4-mercaptohexan-3-one oxime;
(1,2-diphenyl-2-mercaptoethanone oxime);
1,2-di(trifluoromethyl)-2-mercaptoethanone oxime;
1,2-dicyclohexyl-2-merc- aptoethanone oxime;
1,2-dinorbornyl-2-mercaptoethanone oxime; 2-mercaptobenzaldehyde
oxime; 2-mercapto-1-naphthaldehyde oxime; thiophene-2-aldoxime;
methyl 2-thiophenyl ketoxime; and phenyl 2-thiophenyl ketoxime.
[0564] N--S Valence Stabilizer #18: Examples of 2-nitrothiophenols
(2-nitrobenzenethiols) (N--S Bidentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 2-nitrothiophenol;
2,3-dinitrothiophenol; 2,4-dinitrothiophenol;
2,5-dinitrothiophenol; 2,6-dinitrothiophenol;
1-nitro-2-naphthalenethiol; and 2-nitro-1-naphthalenethiol.
[0565] N--S Valence Stabilizer #19: Examples of
2-nitrilothiophenols (2-nitrilobenzenethiols) (N--S Bidentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: 2-cyanothiophenol; 2,3-dicyanothiophenol;
2,4-dicyanothiophenol; 2,5-dicyanothiophenol;
2,6-dicyanothiophenol; 1-cyano-2-naphthalenethiol; and
2-cyano-1-naphthalenethiol.
[0566] N--S Valence Stabilizer #20: Examples of thiohydrazides,
bis(thiohydrazides), and poly(thiohydrazides) (N--S Bidentates and
N--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: thioformic hydrazide; thioacetic hydrazide;
thiopropionic hydrazide; thiobenzoic hydrazide;
thiophthalhydrazide; thiosalicylic hydrazide; thionaphthoic
hydrazides; thionorbornaneacetic hydrazide; thionicotinic
hydrazide; and thioisonicotinic hydrazide. [Note: Thiohydrazides
prefer complexation with lower oxidation states in metal ions.]
[0567] N--S Valence Stabilizer #21: Examples of thiosemicarbazides,
bis(thiosemicarbazides), and poly(thiosemicarbazides) (N--S
Bidentates, N--S Tetradentates, and N--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiosemicarbazide (tsc); thiosemicarbazide diacetic acid (tsda);
1-methylthiosemicarbazide (1 mts); 1-ethylthiosemicarbazide;
1-isopropylthiosemicarbazide; 1-phenylthiosemicarbazide (1
pts)(cryogenine); 1-benzylthiosemicarbazide;
1-cyclohexylthiosemicarbazide; 1-norbornylthiosemicarbazide;
4-methylthiosemicarbazide (4mts); 4-ethylthiosemicarbazide;
4-isopropylthiosemicarbazide; 4-phenylthiosemicarbazide (4-pts);
4-benzylthiosemicarbazide; 4-cyclohexylthiosemicarbazide;
4-norbornylthiosemicarbazide; nicotinic thiosemicarbazide;
isonicotinic thiosemicarbazide; and
4-phenyl-1-benzenesulfonyl-3-thiosemicarbazide (pbst). [Note:
Thiosemicarbazides prefer complexation with lower oxidation states
in metal ions.]
[0568] N--S Valence Stabilizer #22: Examples of five-, seven-, or
nine-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen (usually amine
or imine groups) or sulfur (usually thiols, mercaptans, or
thiocarbonyls) and are not contained in component heterocyclic
rings (N--S Tridentates, N--S Tetradentates, and N--S Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+ include, but are not
limited to: triazadithiacyclodecane ([10]aneS.sub.2N.sub.3);
triazadithiacycloundecane ([11]aneS.sub.2N.sub.3);
triazadithiacyclododecane ([12]aneS.sub.2N.sub.3);
triazadithiacyclotridecane ([13]aneS.sub.2N.sub.3);
triazadithiacyclotetradecane ([14]aneS.sub.2N.sub.3);
triazadithiacyclopentadecane ([15]aneS.sub.2N.sub.3);
thiomorpholine; and thiazolidine.
[0569] N--S Valence Stabilizer #23: Examples of five- or
seven-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen or sulfur and
are contained in component heterocyclic rings (N--S Bidentates,
N--S Tridentates, N--S Tetradentates, or N--S Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dithiopyrantripyridines; dithiophenetripyrroles;
trithiopyrantetrapyridines; and trithiophenetetrapyrroles.
[0570] N--S Valence Stabilizer #24: Examples of five-, seven-, or
nine-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen or sulfur and
are contained in a combination of heterocyclic rings and amine,
imine, thiol, mercapto, or thiocarbonyl groups (N--S Bidentates,
N--S Tridentates, N--S Tetradentates, or N--S Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
azathiapentaphyrins; diazadithiapentaphyrins; azathiapentaphyrins;
and diazadithiapentaphyrins- .
[0571] N--O Valence Stabilizer #1: Examples of imidates,
diimidates, polyimidates, and derivatives of imidic acid (N--O
bidentates and N--O tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: O-methyl formimidate;
O-ethyl formimidate; O-methyl acetimidate; O-ethyl acetimidate;
O-methyl benzimidate; O-ethyl benzimidate; O-methyl
cyclohexylimidate; O-ethyl cyclohexylimidate; O-methyl
pentafluorobenzimidate; O-ethyl pentafluorobenzimidate; O-methyl
2-pyridylimidate; O-ethyl 2-pyridylimidate; O,O'-dimethyl
benzdiimidate; O,O'-dimethyl tetrafluorobenzdiimidate;
2-iminotetrahydrofuran; and 2-iminotetrahydropyran. [Note: Most
imidate complexes are decomposed by water, but their stability can
be enhanced through the use of fluorinated solubility control
anions (e.g. PF.sub.6.sup.-).]
[0572] N--O Valence Stabilizer #2: Examples of pseudoureas,
bis(pseudoureas), and poly(pseudoureas) (N--O bidentates and N--O
tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: O-methyl pseudourea; O-ethyl pseudourea;
O-isopropyl pseudourea; O-benzyl pseudourea; O-cyclohexyl
pseudourea; O-norbornyl pseudourea; O-pentafluorobenzyl pseudourea;
N-methyl pseudourea; N-ethyl pseudourea; N-isopropyl pseudourea;
N-benzyl pseudourea; N-cyclohexyl pseudourea; N-norbornyl
pseudourea; and N-pentafluorobenzyl pseudourea.
[0573] N--O Valence Stabilizer #3: Examples of 2-amidinoacetates,
bis(2-amidinoacetates), and poly(2-amidinoacetates) (N--O
Bidentates and N--O Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
N-methyl-2-amidinoacetate; O-methyl-2-amidinoacetate;
N-benzyl-2-amidinoacetate; and O-benzyl-2-amidinoacetate. [Note:
many 2-amidinoacetates tend to hydrolyze in water. This can be
minimized through the use of fluorinated solubility control anions
such as PF.sub.6.sup.-.]
[0574] N--O Valence Stabilizer #4: Examples of ureas, bis(ureas),
and poly(ureas), including urylene complexes (N--O bidentates and
N--O tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: urea; methylurea; ethylurea; isopropylurea;
benzylurea; cyclohexylurea; naphthylurea; biphenylurea;
norbornylurea; adamantylurea; N,N'-dimethylurea; N,N'-diethylurea;
N,N'-diisopropylurea; N,N'-dibenzylurea; N,N'-dicyclohexylurea;
N,N'-dinapthylurea; N,N'-dibipbenylurea; N,N'-dinorbornylurea;
N,N'-diadamantylurea; ethyleneurea (2-imidazolidone);
propyleneurea; glycoluril (acetyleneurea); and
N,N'-bis(4-nitrophenyl)urea.
[0575] N--O Valence Stabilizer #5: Examples of phosphonimidic-acid,
bis(phosphonimidic acid), poly(phosphonimidic acid), and
derivatives thereof (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphonimidic acid; O-phenylphosphonimidic acid;
O-benzylphosphonimidic acid; O-cyclohexylphosphonimidic acid; and
O-norbornylphosphonimidic acid. [Note: The phosphite (P.sup.+3)
valence of the phosphorus atom makes stabilizization of high
valence metal ions much more difficult, though still possible.]
[0576] N--O Valence Stabilizer #6: Examples of phosphonamidic acid,
phosphonic diamide, bis(phosphonamidic acid), bis(phosphonic
diamide), poly(phosphonamidic acid), poly(phosphonic diamide), and
derivatives thereof (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
phosphonamidic acid, phosphonic diamide, phosphonamidic hydrazide,
phosphonic dihydrazide, O-phenylphosphonamidic acid,
O-benzylphosphonamidic acid, O-cyclohexylphosphonamidic acid,
O-norbornylphosphonamidic acid, N-benzylphosphonic diamide,
N-phenylphosphonic diamide, N-cyclohexylphosphonic diamide, and
N-norbornylphosphonic diamide. [Note: The phosphite (P.sup.+3)
valence of the phosphorus atom makes stabilizization of high
valence metal ions much more difficult, though still possible.]
[0577] N--O Valence Stabilizer #7: Examples of beta-ketoamines
(N-substituted 3-amino-2-propenals), bis(beta-ketoamines), and
poly(beta-ketoamines) (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
4-methylamino-3-penten-2-one; 4-ethylamino-3-penten-2-one;
4-isopropylamino-3-penten-2-one; 4-phenylamino-3-penten-2-one;
4-naphthylamino-3-penten-2-one; 4-cyclohexylamino-3-penten-2-one;
4-norbornylamino-3-penten-2-one; 4-hydroxyamino-3-penten-2-one;
3-methylamino-1-phenyl-2-butenal; 3-ethylamino-1-phenyl-2-butenal;
3-isopropylamino-1-phenyl-2-butenal;
3-phenylamino-1-phenyl-2-butenal;
3-naphthylamino-1-phenyl-2-butenal;
3-cyclohexylamino-1-phenyl-2-butenal;
3-norbornylamino-1-phenyl-2-butenal;
3-hydroxyamino-1-phenyl-2-butenal;
3-phenylamino-1,3-diphenyl-2-propenal;
3-cyclohexylamino-1,3-dicyclohexyl- -2-propenal;
3-norbornylamino-1,3-dinorbornyl-2-propenal; 2,2'-pyridil;
alpha-pyridoin; 4-aminoantipyrine (aap);
beta-phenylaminopropiophenone; and polyaminoquinones (PAQs).
[0578] N--O Valence Stabilizer #8: Examples of 3-aminoacrylamides
(3-amino-2-propenamides), 3,3-diaminoacrylamides,
bis(3-aminoacrylamides)- , bis(3,3-diaminoacrylamides),
poly(3-aminoacrylamides), and poly(3,3-diaminoacrylamides) (N--O
Bidentates and N--O Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: 3-methylaminoacrylamide;
3-ethylaminoacrylamide, 3-isopropylaminoacrylami- de,
3-phenylaminoacrylamide; 3-naphthylaminoacrylamide;
3-cyclohexylaminoacrylamide; 3-norbornylaminoacrylamide;
3-hydroxyaminoacrylamide; N-methyl-3-methylaminoacrylamide;
N-ethyl-3-ethylaminoacrylamide,
N-isopropyl-3-isopropylaminoacrylamide,
N-phenyl-3-phenylaminoacrylamide;
N-naphthyl-3-naphthylaminoacrylamide;
N-cyclohexyl-3-cyclohexylaminoacrylamide;
N-norbornyl-3-norbornylaminoacr- ylamide;
3-amino-3-methylaminoacrylamide; 3-amino-3-ethylaminoacrylamide,
3-amino-3-isopropylaminoacrylamide,
3-amino-3-phenylaminoacrylamide; 3-amino-3-naphthylaminoacrylamide;
3-amino-3-cyclohexylaminoacrylamide;
3-amino-3-norbornylaminoacrylamide; and
3-amino-3-hydroxyaminoacrylamide.
[0579] N--O Valence Stabilizer #9: Examples of 3-aminoacrylic acids
(3-amino-2-propenoic acids), 3-hydroxy-3-aminoacrylic acids,
bis(3-aminoacrylic acids), bis(3-hydroxy-3-aminoacrylic acids),
poly(3-aminoacrylic acids), and poly(3-hydroxy-3-aminoacrylic
acids), and derivatives thereof (N--O Bidentates and N--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 3-aminoacrylic acid; 3-hydroxy-3-aminoacrylic acid;
3-methylaminoacrylic acid; 3-ethylaminoacrylic acid;
3-isopropylaminoacrylic acid; 3-phenylaininoacrylic acid;
3-naphthylaminoacrylic acid; 3-cyclohexylaminoacrylic acid;
3-norbornylaminoacrylic acid; 3-hydroxyaminoacrylic acid; methyl
3-methylaminoacrylate; ethyl 3-ethylaminoacrylate; isopropyl
3-isopropylaminoacrylate; benzyl 3-phenylaminoacrylate; naphthyl
3-naphthylaminoacrylate; cyclohexyl 3-cyclohexylaminoacrylate; and
norbornyl 3-norbornyl aminoacryl ate.
[0580] N--O Valence Stabilizer #10: Examples of N-acyl
benzylidenimines, bis(N-acyl benzylidenimines), and poly(N-acyl
benzylidenimines) (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N-formyl benzylidenimine, N-acetyl benzylidenimine; N-benzoyl
benzylidenimine; and N-pentafluorobenzoyl benzylidenimine.
[0581] N--O Valence Stabilizer #11: Examples of 2-nitroanilines
(N--O Bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+ include,
but are not limited to: 2-nitroaniline; 2,6-dintroaniline;
2-nitrophenylenediamine; 2-nitrophenylenetriamine;
2-nitro-1-aminonaphthalene; 1-nitro-2-aminonaphthalene;
nitrodiaminonaphthalene; and dipicrylamine.
[0582] N--O Valence Stabilizer #12: Examples of 2-nitrilophenols
(N--O Bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: 2-cyanophenol; 2,3-dicyanophenol;
2,4-dicyanophenol; 2,5-dicyanophenol; 2,6-dicyanophenol;
1-cyano-2-naphthol; and 2-cyano-1-naphthol. Also includes
acylcyanamides.
[0583] N--O Valence Stabilizer #13: Examples of amine N-oxides and
N-diazine oxides (azoxy compounds) (N--O Bidentates, N--O
Tridentates, and N--O Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: pyridine N-oxide (pyNO
or PNO); picoline N-oxide (picNO); lutidine N-oxide (lutNO or LNO);
collidine N-oxide (collNO or CNO); quinoline N-oxide (QuinNO or
QNO); isoquinoline N-oxide (isoQuinNO or IQNO); acridine N-oxide
(AcrNO or ANO); picolinic acid N-oxide (PicANO); pyridinethiolate
N-oxide (PTNO); adenine N-oxide; adenosine N-oxide;
1,10-phenanthroline mono-N-oxide (phenNO); 1,10-phenanthroline
N,N-dioxide (phen2NO); bipyridyl mono-N-oxide (bipyNO); bipyridyl
N,N-dioxide (bipy2NO); pyrazine mono-N-oxide (pyzNO); pyrazine
N,N-dioxide (pyz2NO); pyrimidine mono-N-oxide (pymNO); pyrimidine
N,N-dioxide (pym2NO); pyridazine mono-N-oxide (pdzNO); pyridazine
N,N-dioxide (pdz2NO); quinoxaline mono-N-oxide (qxNO); quinoxaline
N,N-dioxide (qx2NO); phenazine mono-N-oxide (phzNO); phenazine
N,N-dioxide (phz2NO); 2,3-di(pyridine N-oxide)quinoxaline (dpoq);
inosine N-oxide; 4,4'-bipyridine N,N-dioxide; 1-hydroxypyrazole
2-oxide; 1-hydroxyimidazole 3-oxide; 2,2'-diimidazyl 3,-3'-dioxide;
imidazole N-oxides; lIhydroxyimidazole-3-N-oxides; N-benzylidine
aniline N-oxide; N-(naphthylidene) aniline N-oxide;
N-(hydroxybenzylidene) aniline N-oxide; and 2,2'-dibenzimidazyl
3,3'-dioxide (indigo N,N-dioxide) for amine N-oxides; and
azoxybenzene; phthalazine N-oxide; benzocinnoline N-oxide; and
bipyrazinyl N-oxide as N-diazine oxide examples.
[0584] N--O Valence Stabilizer #14: Examples of hydrazides,
bis(hydrazides), and poly(hydrazides) (N--O Bidentates and N--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: formic hydrazide; acetic hydrazide; propionic
hydrazide; benzoic hydrazide; phthalhydrazide; salicylic hydrazide;
naphthoic hydrazides; norbornaneacetic hydrazide; nicotinic
hydrazide; and isonicotinic hydrazide (isoniazid). [Note:
Hydrazides prefer complexation with lower oxidation states in metal
ions.]
[0585] N--O Valence Stabilizer #15: Examples of semicarbazides,
bis(semicarbazides), and poly(semicarbazides) (N--O Bidentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
semicarbazide (sc); semicarbazide diacetic acid (sda);
1-methylsemicarbazide; 1-ethylsemicarbazide;
1-isopropylsemicarbazide; 1-phenylsemicarbazide;
1-benzylsemicarbazide; 1-cyclohexylsemicarbazide;
1-norbornylsemicarbazide; 4-methylsemicarbazide;
4-ethylsemicarbazide; 4-isopropylsemicarbazide;
4-phenylsemicarbazide; 4-benzylsemicarbazide;
4-cyclohexylsemicarbazide; 4-norbornylsemicarbazide; nicotinic
semicarbazide; and isonicotinic semicarbazide. [Note:
Semicarbazides prefer complexation with lower oxidation states in
metal ions.]
[0586] N--O Valence Stabilizer #16: Examples of five-, seven-, or
nine-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen (usually amine
or imine groups) or oxygen (usually hydroxy, carboxy, or carbonyl
groups) and are not contained in component heterocyclic rings (N--O
Tridentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+ include, but are not limited to:
triazadioxacyclodecane ([10]aneO.sub.2N.sub.3);
triazadioxacycloundecane ([11]aneO.sub.2N.sub.3)- ;
triazadioxacyclododecane ([12]aneO.sub.2N.sub.3);
triazadioxacyclotridecane ([13]aneO.sub.2N.sub.3);
triazadioxacyclotetradecane ([14]aneO.sub.2N.sub.3); and
triazadioxacyclopentadecane ([15]aneO.sub.2N.sub.3).
[0587] N--O Valence Stabilizer #17: Examples of five- or
seven-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen or oxygen and
are contained in component heterocyclic rings (N--O Bidentates,
N--O Tridentates, N--O Tetradentates, or N--O Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dipyrantripyridines; difurantripyrroles; tripyrantetrapyridines;
and trifurantetrapyrroles.
[0588] N--O Valence Stabilizer #18: Examples of five-, seven-, or
nine-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen or oxygen and
are contained in a combination of heterocyclic rings and amine,
imine, hydroxy, carboxy, or carbonyl groups (N--O Bidentates, N--O
Tridentates, N--O Tetradentates, or N--O Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
azaoxapentaphyrins; diazadioxapentaphyrins; azaoxapentaphyrins; and
diazadioxapentaphyrins.
[0589] S--O Valence Stabilizer #1: Examples of thiobiurets
(thioimidodicarbonic diamides), thioisobiurets, thiobiureas,
thiotriurets, thiotriureas, bis(thiobiurets), bis(thioisobiurets),
bis(thiobiureas), poly(thiobiurets), poly(thioisobiurets),
poly(thiobiureas) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates), and (3-formamidino thiocarbamides) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiobiuret, thioisobiuret, thiobiurca, thiotriuret, thiotriurea,
nitrothiobiuret, dinitrothiobiuret, aminothiobiuret,
diaminothiobiuret, oxythiobiuret, dioxythiobiuret, cyanothiobiuret,
methylthiobiuret, ethylthiobiuret, isopropylthiobiuret,
phenylthiobiuret, benzylthiobiuret, cyclohexylthiobiuret,
norbornylthiobiuret, adamantylthiobiuret, dimethylthiobiuret,
diethylthiobiuret, dicyclohexylthiobiuret, dinorbornylthiobiuret,
and diadamantylthiobiuret.
[0590] S--O Valence Stabilizer #2: Examples of acylthioureas,
aroylthioureas, thioacylureas, thioaroylureas, bis(acylthioureas),
bis(aroylthioureas), bis(thioacylureas) bis(thioaroylureas),
poly(thioacylthioureas), poly(thioaroylthioureas),
poly(thioacylureas), and poly(thioaroylureas) (S--O Bidentates,
S--O Tridentates, S--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: thioformylurea,
thioacetylurea, thiobenzoylurea, thiocyclohexoylurea,
pentafluorothiobenzoylurea, acetylthiourea, benzoylthiourea, and
cyclohexoylthiourea.
[0591] S--O Valence Stabilizer #3: Examples of
thioimidodialdehydes, thiohydrazidodialdehydes (thioacyl
hydrazides), bis(thioimidodialdehydes)- ,
bis(thiohydrazidodialdehydes), poly(thioimidodialdehydes), and
poly(thiohydrazidodialdehydes) (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: thiodiacetamide, thiodipropanamide,
thiodibutanamide, thiodibenzamide, and thiodicyclohexamide.
[0592] S--O Valence Stabilizer #4: Examples of thioimidodicarbonic
acids, thiohydrazidodicarbonic acids, bis(thioimidodicarbonic
acids), bis(thiohydrazidodicarbonic acids),
poly(thioimidodicarbonic acids), poly(thiohydrazidodicarbonic
acids) and derivatives thereof (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: thioimidodicarbonic acid,
thiohydrazidodicarbonic acid, O-phenylthioimidodicarbonic acid,
O-benzylthioimidodicarbonic acid, O-cyclohexylthioimidodicarbonic
acid, O-norbornylthioimidodicarbonic acid,
O,O'-diphenylthioimidodicarbonic acid,
O,O'-dibenzylthioimidodicarbonic acid,
O,O'-dicyclohexylthioimidodi- carbonic acid,
O,O'-dinorbornylthioimidodicarbonic acid.
[0593] S--O Valence Stabilizer #5: Examples of 1,2-monothioketones
(monothiolenes, monothio-alpha-ketonates), 1,2,3-monothioketones,
1,2,3-dithioketones, monothiotropolonates, ortho-monothioquinones,
bis(1,2-monothioketones), and poly(1,2-monothioketones) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
monothiotropolone; 1,2-monothiobenzoquinone (o-monothioquinone);
di-tert-butyl-1,2-monothiob- enzoquinone;
hexafluoro-1,2-monothiobenzoquinone; 1,2-monothionaphthoquino- ne;
9,10-monothiophenanthroquinone; monothiosquaric acid;
monothiodeltic acid; monothiocroconic acid; and monothiorhodizonic
acid.
[0594] S--O Valence Stabilizer #6: Examples of
trithioperoxydicarbonic diamides, bis(trithioperoxydicarbonic
diamides), and poly(trithioperoxydicarbonic diamides) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
trithioperoxydicarbonic diamide; N-phenyltrithioperoxydicarbonic
diamide; N-benzyltrithioperoxydicarbonic diamide;
N-cyclohexyltrithioperoxydicarbonic diamide;
N-norbornyltrithioperoxydicarbonic diamide;
N,N'-diphenyltrithioperoxydic- arbonic diamide;
N,N'-dibenzyltrithioperoxydicarbonic diamide;
N,N'-dicyclohexyltrithioperoxydicarbonic diamide; and
N,N'-dinorbornyltrithioperoxydicarbonic diamide.
[0595] S--O Valence Stabilizer #7: Examples of dithiodicarbonic
acids, bis(dithiodicarbonic acids), poly(dithiodicarbonic acids),
and derivatives thereof (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: dithiodicarbonic acid, O-phenyldithiodicarbonic
acid, O-benzyldithiodicarbonic acid, O-cyclohexyldithiodicarbonic
acid, O-norbornyldithiodicarbonic acid,
O,O'-diphenyldithiodicarbonic acid, O,O'-dibenzyldithiodicarbonic
acid, O,O'-dicyclohexyldithiodicarbonic acid, and
O,O'-dinorbornyldithiodicarbonic acid.
[0596] S--O Valence Stabilizer #8: Examples of
trithioperoxydicarbonic acids, bis(trithioperoxydicarbonic acids),
poly(trithioperoxydicarbonic acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
-trithioperoxydicarbonic acid, O-phenyltrithioperoxydicarboni- c
acid; O-benzyltrithioperoxydicarbonic acid;
O-cyclohexyltrithioperoxydic- arbonic acid;
O-norbornyltrithioperoxydicarbonic acid;
O,O'-diphenyltrithioperoxydicarbonic acid;
O,O'-dibenzyltrithioperoxydica- rbonic acid;
O,O'-dicyclohexyltrithioperoxydicarbonic acid; and
O,O'-dinorbornyltrithioperoxydicarbonic acid.
[0597] S--O Valence Stabilizer #9: Examples of
monothioperoxydiphosphorami- des,
bis(monothioperoxydiphosphoramides), and
poly(monothioperoxydiphospho- ramides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: monothioperoxydiphosphoramide,
N-methylmonothioperoxydiphosphoramide,
N-isopropylmonothioperoxydiphosphoramide,
N-tert-butylmonothioperoxydipho- sphoramide,
N-phenylmonothioperoxydiphosphoramide, N-pentafluorophenylmono-
thioperoxydiphosphoramide, N-benzylmonothioperoxydiphosphoramide,
N-cyclohexylmonothioperoxydiphosphoramide,
N-norbornylmonothioperoxydipho- sphoramide,
N,N'"-dimethylmonothioperoxydiphosphoramide,
N,N'"-diisopropylmonothioperoxydiphosphoramide,
N,N'"-di-tert-butylmonoth- ioperoxydiphosphoramide,
N,N'"-diphenylmonothioperoxydiphosphoramide,
N,N'"-di-pentafluorophenylmonothioperoxydiphosphoramide,
N,N'"-dibenzylmonothioperoxydiphosphoramide,
N,N'"-dicyclohexylmonothiope- roxydiphosphoramide, and
N,N'"-dinorbornylmonothioperoxydiphosphoramide.
[0598] S--O Valence Stabilizer #10: Examples of
monothioperoxydiphosphoric acids, bis(monothioperoxydiphosphoric
acids), poly(monothioperoxydiphosph- oric acids), and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: monothioperoxydiphosphoric acid,
methylmonothioperoxydiphosph- oric acid,
isopropylmonothioperoxydiphosphoric acid,
tert-butylmonothioperoxydiphosphoric acid,
phenylmonothioperoxydiphosphor- ic acid,
pentafluorophenylmonothioperoxydiphosphoric acid,
benzylmonothioperoxydiphosphoric acid,
cyclohexylmonothioperoxydiphosphor- ic acid,
norbornylmonothioperoxydiphosphoric acid, dimethylmonothioperoxyd-
iphosphoric acid, diisopropylmonothioperoxydiphosphoric acid,
di-tert-butylmonothioperoxydiphosphoric acid,
diphenylmonothioperoxydipho- sphoric acid,
di-pentafluorophenylmonothioperoxydiphosphoric acid,
dibenzylmonothioperoxydiphosphoric acid,
dicyclohexylmonothioperoxydiphos- phoric acid, and
dinorbornylmonothioperoxydiphosphoric acid.
[0599] S--O Valence Stabilizer #11: Examples of
monothioimidodiphosphonic acids, monothiohydrazidodiphosphonic
acids, bis(monothioimidodiphosphonic acids),
bis(monothiohydrazidodiphosphonic acids), poly(monothioimidodipho-
sphonic acids), poly(monothiohydrazidodiphosphonic acids), and
derivatives thereof (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: monothioimidodiphosphonic acid,
methylmonothioimidodiphosphonic acid,
isopropylmonothioimidodiphosphonic acid,
tert-butylmonothioimidodiphospho- nic acid,
phenylmonothioimidodiphosphonic acid, pentafluorophenylmonothioi-
midodiphosphonic acid, benzylmonothioimidodiphosphonic acid,
cyclohexylmonothioimidodiphosphonic acid,
norbornylmonothioimidodiphospho- nic acid,
dimethylmonothioimidodiphosphonic acid, diisopropylmonothioimido-
diphosphonic acid, di-tert-butylmonothioimidodiphosphonic acid,
diphenylmonothioimidodiphosphonic acid,
di-pentafluorophenylmonothioimido- diphosphonic acid,
dibenzylmonothioimidodiphosphonic acid,
dicyclohexylmonothioimidodiphosphonic acid, and
dinorbornylmonothioimidod- iphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0600] S--O Valence Stabilizer #12: Examples of
monothioimidodiphosphonami- des, monothiohydrazidodiphosphonamides,
bis(monothioimidodiphosphonamides)- ,
bis(monothiohydrazidodiphosphonamides),
poly(monothioimidodiphosphonamid- es), and
poly(monothiohydrazidodiphosphonamides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: monothioimidodiphosphonamide,
N-methylmonothioimidodiphosphonamide,
N-isopropylmonothioimidodiphosphona- mide,
N-tert-butylmonothioimidodiphosphonamide,
N-phenylmonothioimidodipho- sphonamide,
N-pentafluorophenylmonothioimidodiphosphonamide,
N-benzylmonothioimidodiphosphonamide,
N-cyclohexylmonothioimidodipbosphon- amide,
N-norbornylmonothioimidodiphosphonamide,
N,N'"-dimethylmonothioimid- odiphosphonamide,
N,N'"-diisopropylmonothioimidodiphosphonamide,
N,N'"-di-tert-butylmonothioimidodiphosphonamide,
N,N'"-diphenylmonothioim- idodiphosphonamide,
N,N'"-di-pentafluorophenylmonothioimidodiphosphonamide- ,
N,N'"-dibenzylmonothioimidodiphosphonamide,
N,N'"-dicyclohexylmonothioim- idodiphosphonamide, and
N,N'"-dinorbornylmonothioimidodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0601] S--O Valence Stabilizer #13: Examples of
dithiodiphosphonamides, bis(dithiodiphosphonamides), and
poly(dithiodiphosphonamides) (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiodiphosphonamide,
N-methyldithiodiphosphonamide, N-isopropyldithiodiphosphonamide,
N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide,
N-pentafluorophenyldithiodiphosphonamide,
N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide,
N-norbornyldithiodiphosphonamide, N,N'"-dimethyldithiodiphosphonami
de, N,N'"-diisopropyldithiodiphosphonam- ide,
N,N'"-di-tert-butyldithiodiphosphonamide,
N,N'"-diphenyldithiodiphosp- honamide,
N,N'"-di-pentafluorophenyldithiodiphosphonamide,
N,N'"-dibenzyldithiodiphosphonamide,
N,N'"-dicyclohexyldithiodiphosphonam- ide, and
N,N'"-dinorbornyldithiodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0602] S--O Valence Stabilizer #14: Examples of dithiodiphosphonic
acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic
acids), and derivatives thereof (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiodiphosphonic acid,
methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid,
tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid,
pentafluorophenyldithiodiphosphonic acid, benzyldthiodiphosphonic
acid, cyclohexyldithiodiphosphonic acid norbornyldithiodiphosphonic
acid, dimethyldithiodiphosphonic acid,
diisopropyldiothiodiphosphonic acid,
di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic
acid, di-pentafluorophenyldithiodiphosph- onic acid,
dibenzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic
acid, and dinorbornyldithiodiphosphoric acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0603] S--O Valence Stabilizer #15: Examples of
monothioperoxydiphosphonam- ides,
bis(monothioperoxydiphosphonamides), and
poly(monothioperoxydiphosph- onamides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: monothioperoxydiphosphonamide,
N-methylmonothioperoxydiphosphonamide,
N-isopropylmonothioperoxydiphosphonamide,
N-tert-butylmonothioperoxydipho- sphonamide,
N-phenylmonothioperoxydiphosphonamide, N-pentafluorophenylmono-
thioperoxydiphosphonamide, N-benzylmonothioperoxydiphosphonamide,
N-cyclohexylmonothioperoxydiphosphonamide,
N-norbornylmonothioperoxydipho- sphonamide,
N,N'"-dimethylmonothioperoxydiphosphonamide,
N,N'"-diisopropylmonothioperoxydiphosphonamide,
N,N'"-di-tert-butylmonoth- ioperoxydiphosphonamide,
N,N'"-diphenylmonothioperoxydiphosphonamide,
N,N'"-di-pentafluorophenylmonothioperoxydiphosphonamide,
N,N'"-dibenzylmonothioperoxydiphosphonamide,
N,N'"-dicyclohexylmonothiope- roxydiphosphonamide, and
N,N'"-dinorbornylmonothioperoxydiphosphonamide. [Note: The
phosphite (p+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.]
[0604] S--O Valence Stabilizer #16: Examples of
monothioperoxydiphosphonic acids, bis(monothioperoxydiphosphonic
acids), poly(monothioperoxydiphosph- onic acids), and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: monothioperoxydiphosphonic acid,
methylmonothioperoxydiphosph- onic acid,
isopropylmonothiopcroxydiphosphonic acid,
tert-butylmonothioperoxydiphosphonic acid,
phenylmonothioperoxydiphosphon- ic acid,
pentafluorophenylmonothioperoxydiphosphonic acid,
benzylmonothioperoxydiphosphonic acid,
cyclohexylmonothioperoxydiphosphon- ic acid,
norbornylmonothioperoxydiphosphonic acid, dimethylmonothioperoxyd-
iphosphonic acid, diisopropylmonothioperoxydiphosphonic acid,
di-tert-butylmonothioperoxydiphosphonic acid,
diphenylmonothioperoxydipho- sphonic acid,
di-pentafluorophenylmonothioperoxydiphosphonic acid,
dibenzylmonothioperoxydiphosphonic acid,
dicyclohexylmonothioperoxydiphos- phonic acid, and
dinorbornylmonothioperoxydiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0605] S--O Valence Stabilizer #17: Examples of monothiophosphoric
acids (phosphorothioic acids), bis(monothiophosphoric acids),
poly(monothiophosphoric acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
monothiophosphoric acid, O-phenylmonothiophosphoric acid,
O-benzylmonothiophosphoric acid, O-cyclohexylmonothiophosphoric
acid, O-norbornylmonothiophosphoric acid,
O,O-diphenylmonothophosphoric acid, O,O-dibenzylmonothiophosphoric
acid, O,O-dicyclohexylmonothiophosphoric acid, and
O,O-dinorbornylmonothiophosp- horic acid.
[0606] S--O Valence Stabilizer #18: Examples of
phosphoro(dithioperoxoic) acids, bis[phosphoro(dithioperoxoic)
acids], poly[phosphoro(dithioperoxoi- c) acids], and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: phosphoro(dithioperoxoic) acid,
O-phenylphosphoro(dithioperox- oic) acid,
O-benzylphosphoro(dithioperoxoic) acid, O-cyclohexylphosphoro(d-
ithioperoxoic) acid, O-norbornylphosphoro(dithioperoxoic) acid,
O,O-diphenylphosphoro(dithioperoxoic) acid,
O,O-dibenzylphosphoro(dithiop- eroxoic) acid,
O,O-dicyclohexylphosphoro(dithioperoxoic) acid, and
O,O-dinorbornylphosphoro(dithioperoxoic) acid.
[0607] S--O Valence Stabilizer #19: Examples of monothiophosphonic
Acids (phosphonothioic acids), bis(monothiophosphonic acids),
poly(monothiophosphonic acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
monothiophosphonic acid, O-phenylmonothiophosphonic acid,
O-benzylmonothiophosphonic acid,
.beta.-cyclohexylmonothiophosphonic acid,
O-norbornylmonothiophosphonic acid, O,P-diphenylmonothiophosphonic
acid, O,P-dibenzylmonothiophosphonic acid,
O,P-dicyclohexylmonothiophosphonic acid, and
O,P-dinorbornylmonothiophosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0608] S--O Valence Stabilizer #20: Examples of
phosphono(dithioperoxoic) acids, bis[phosphono(dithioperoxoic)
acids], poly[phosphono(dithioperoxoi- c) acids], and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: phosphono(dithioperoxoic) acid,
O-phenylphosphono(dithioperox- oic) acid,
O-benzylphosphono(dithioperoxoic) acid, O-cyclohexylphosphono(d-
ithioperoxoic) acid, O-norbornylphosphono(dithioperoxoic) acid,
O,P-diphenylphosphono(dithioperoxoic) acid,
O,P-dibenzylphosphono(dithiop- eroxoic) acid,
O,P-dicyclohexylphosphono(dithioperoxoic) acid, and
O,P-dinorbornylphosphono(dithioperoxoic) acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.]
[0609] S--O Valence Stabilizer #21: Examples of
beta-hydroxythioketones, beta-hydroxythioaldehydes,
bis(beta-hydroxythioketones), bis(beta-hydroxythioaldehydes),
poly(beta-hydroxythioketones), and poly(beta-hydroxythioaldehydes)
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
4-hydroxypentan-2-thione; 1,3-diphenyl-3-hydroxypropanethioal-
dehyde; 1,3-dibenzyl-3-hydroxypropanethioaldehyde;
1,3-dicyclohexyl-3-hydr- oxypropanethioaldehyde;
1,3-dinorbornyl-3-hydroxypropanethioaldehyde;
1,3-di(2-thienyl)-3-hydroxypropanethioaldehyde;
1,3-di(2-furyl)-3-hydroxy- propanethioaldehyde;
1-hydroxythioacetophenone; and beta-hydroxythiobenzophenone.
[0610] S--O Valence Stabilizer #22: Examples of
beta-mercaptoketones, beta-mercaptoaldehydes,
bis(beta-mercaptoketones), bis(beta-mercaptoaldehydes),
poly(beta-mercaptoketones), and poly(beta-mercaptoaldehydes) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
4-mercaptopentan-2-one; 1,3-diphenyl-3-mercaptopropanal;
1,3-dibenzyl-3-mercaptopropanal;
1,3-dicyclohexyl-3-mercaptopropanal;
1,3-dinorbornyl-3-mercaptopropanal;
1,3-di(2-thienyl)-3-mercaptopropanal;
1,3-di(2-furyl)-3-mercaptopropanal;
3-mercapto-1,5-pentanedialdehyde; o-mercaptoacetophenone;
5-mercapto-1,4-naphthoquinone; 1-mercaptoacridone;
1-mercaptoanthraquinone; 1,8-dimercaptoanthraquinone; and
beta-mercaptobenzophenone.
[0611] S--O Valence Stabilizer #23: Examples of
N-(aminomethylol)thioureas [N-(aminohydroxymethyl)thioureas],
bis[N-(aminomethylol)thioureas], and
poly[N-(aminomethylol)thioureas] (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: N'-(aminohydroxymethyl)thiourea;
N,N"-dimethyl-N'-(aminohydro- xymethyl)thiourea;
N,N'-diethyl-N'-(aminohydroxymethyl)thiourea;
N,N"-isopropyl-N'-(aminohydroxymethyl)thiourea;
N,N"-diphenyl-N'-(aminohy- droxymethyl)thiourea;
N,N"-dibenzyl-N'-(aminohydroxymethyl)thiourea;
N,N"-dicyclohexyl-N'-(aminohydroxymethyl)thiourea; and
N,N"-dinorbornyl-N'-(aminohydroxymethyl)thiourea.
[0612] S--O Valence Stabilizer #24: Examples of
N-(aminomethylthiol)ureas [N-(aminomercaptomethyl)ureas],
bis[N-(aminomethylthiol)ureas], and poly[N-(aminomethylthiol)ureas]
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
N'-(aminomercaptomethyl)urea; N,N'-dimethyl-N'-(aminomercapto-
methyl)urea; N,N'-diethyl-N'-(aminomercaptomethyl)urea;
N,N"-isopropyl-N'-(aminomercaptomethyl)urea;
N,N"-diphenyl-N'-(aminomerca- ptomethyl)urea;
N,N"-dibenzyl-N'-(aminomercaptomethyl)urea;
N,N"-dicyclohexyl-N'-(aminomercaptomethyl)urea; and
N,N"-dinorbornyl-N'-(aminomercaptomethyl)urea.
[0613] S--O Valence Stabilizer #25: Examples of monotbiooxamides,
bis(monothiooxamides), and poly(monothiooxamides) (S--O Bidentates,
S--O Tridentates, S--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: monothiooxamide,
N-methylthiooxamide; N-ethylthiooxamide; N-isopropylthiooxamide;
N-phenylthiooxamide; N-benzylthiooxamide; N-cyclohexylthiooxamide;
N-norbornylthiooxamide; N,N'-dimethylthiooxamide;
N,N'-diethylthiooxamide; N,N'-diisopropylthiooxamide;
N,N'-diphenylthiooxamide; N,N'-dibenzylthiooxamide;
N,N'-dicyclohexylthiooxamide; and N,N'-dinorbornylthiooxamide.
[0614] S--O Valence Stabilizer #26: Examples of beta-mercapto
carboxylic acids, bis(beta-mercapto carboxylic acids),
poly(beta-mcrcapto carboxylic acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to: methyl
3-mercaptopropanoate; methyl 3-mercaptobutanoate; ethyl
3-mercaptobutanoate; phenyl 3-mercaptobutanoate; cyclohexyl
3-mercaptobutanoate; norbornyl 3-mercaptobutanoate; methyl
beta-mercaptohydrocinnamate; ethyl beta-mercaptohydrocinnamate;
phenyl beta-mercaptohydrocinnamate; methyl o-mercaptobenzoate;
ethyl o-mercaptobenzoate; phenyl o-mercaptobenzoate; cyclohexyl
o-mercaptobenzoate; (2-benzothiazolylthio) succinic acid (mtbs);
norbornyl o-mercaptobenzoate; and
3-[(benzothiazol-2-yl)thio]propionic acid.
[0615] S--O Valence Stabilizer #27: Examples of beta-mercapto
thiocarboxylic acids, bis(beta-mercapto thiocarboxylic acids),
poly(beta-mercapto thiocarboxylic acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to: methyl
3-mercaptothiobutanoate; ethyl 3-mercaptothiobutanoate; phenyl
3-mercaptothiobutanoate; cyclohexyl 3-mercaptothiobutanoate;
norbornyl 3-mercaptothiobutanoate; methyl
beta-mercaptothiocinnamate; ethyl beta-mercaptothiocinnamate;
phenyl beta-mercaptothiocinnamate; methyl o-mercaptothiobenzoate;
ethyl o-mercaptothiobenzoate; phenyl o-mercaptothiobenzoate;
cyclohexyl o-mercaptothiobenzoate; norbornyl
o-mercaptothiobenzoate; and (alkylthio)oxoethyl alkyl(aryl)
disulfides.
[0616] S--O Valence Stabilizer #28: Examples of beta-hydroxy
thiocarboxylic acids, bis(beta-hydroxy thiocarboxylic acids),
poly(beta-hydroxy thiocarboxylic acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to: methyl
3-hydroxythiobutanoate; ethyl 3-hydroxythiobutanoate; phenyl
3-hydroxythiobutanoate; cyclohexyl 3-hydroxythiobutanoate;
norbornyl 3-hydroxythiobutanoate; methyl beta-hydroxythiocinnamate;
ethyl beta-hydroxythiocinnamate; phenyl beta-hydroxythiocinnamate;
methyl o-hydroxythiobenzoate; ethyl o-hydroxythiobenzoate; phenyl
o-hydroxythiobenzoate; cyclohexyl o-hydroxythiobenzoate; and
norbornyl o-hydroxythiobenzoate.
[0617] S--O Valence Stabilizer #29: Examples of beta-mercapto
carboxamides, bis(beta-mercapto carboxamides), poly(beta-mercapto
carboxamides), and derivatives thereof (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: N-methyl 3-mercaptobutanamide;
N-ethyl 3-mercaptobutanamide; N-phenyl 3-mercaptobutanamide;
N-cyclohexyl 3-mercaptobutanamide; N-norbornyl
3-mercaptobutanamide; N-methyl o-mercaptobenzamide; N-ethyl
o-mercaptobenzamide; N-phenyl o-mercaptobenzamide; N-cyclohexyl
o-mercaptobenzamide; and N-norbornyl o-mercaptobenzamide.
[0618] S--O Valence Stabilizer #30: Examples of
S-alkylthiocarboxylic Acids, S-arylthiocarboxylic Acids, and
S,S-thiobiscarboxylic Acids (S--O Bidentates and S--O Tridentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: (methylthio)acetic acid; (methylthio)benzoic acid;
(methylthio)nicotinic acid; (methylthio)napthoic acid;
(phenylthio)acetic acid; (phenylthio)benzoic acid;
(phenylthio)naphthoic acid; (norbornylthio)acetic acid;
(norbornylthio)benzoic acid; (norbornylthio)napthoic acid;
thiobisacetic acid; thiobisbenzoic acid; and thiobisnapthoic
acid.
[0619] S--O Valence Stabilizer #31: Examples of
S-alkyldisulfidocarboxylic acids, S-aryldisulfidocarboxylic acids,
and S,S'-disulfidobiscarboxylic acids (S--O Bidentates and S--O
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: (methyldisulfido)acetic acid;
(methyldisulfido)benzoic acid; (methyldisulfido)nicotinic acid;
(methyldisulfido)napthoic acid; (phenyldisulfido)acetic acid;
(phenyldisulfido)benzoic acid; (phenyldisulfido)naphthoic acid;
(norbornyldisulfido)acetic acid; (norbornyldisulfido)benzoic acid;
(norbornyldisulfido)napthoic acid; S,S'-disulfidobisacetic acid;
S,S'-disulfidobisbenzoic acid; and S,S'-disulfidobisnapthoic
acid.
[0620] S--O Valence Stabilizer #32: Examples of
monothiomonocarboxylic acids, dithiodicarboxylic acids,
bis(monothiomonocarboxylic acids), bis(dithiodicarboxylic acids),
poly(monothiomonocarboxylic acids), poly(dithiodicarboxylic acids),
and derivatives thereof (S--O Bidentates and S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: thioacetic acid; thiopropionic acid; thiobenzoic acid;
thiophenylacetic acid; thiocyclohexanoic acid; thiofuroic acid;
thionaphthoic acid; phenyl thioacetate; phenyl thiopropionate;
phenyl thiobenzoate; phenyl thiocyclohexanoate; phenyl thiofuroate;
phenyl thionaphthoate; dithiooxalic acid (dto); monothiooxalic acid
(mtox); dithiomalonic acid; dithiosuccinic acid; diphenyl
dithiooxalate; diphenyl dithiomalonate; and diphenyl
dithiosuccinate.
[0621] S--O Valence Stabilizer #33: Examples of monothiocarbonates
and bis(monothiocarbonates) (S--O Bidentates and S--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: S,O-diethyldithiocarbonate;
S,O-diisopropyldithiocarbonate; S,O-diphenyldithiocarbonate;
S,O-dibenzyldithiocarbon ate; S,O-dicyclohexyldithiocarbonate; and
S,O-dinorbornyldithiocarbonate.
[0622] S--O Valence Stabilizer #34: Examples of monothiocarbazates
(monothiocarbazides), bis(monothiocarbazates), and
poly(monothiocarbazates) (S--O Bidentates, S--O Tridentates, and
S--O Tetradentates; or possibly N--S Bidentates, N--S Tridentates,
and N--S Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: N,N'-dimethylmonothiocarbazate;
N,N'-di(trifluoromethyl)monot- hiocarbazate;
N,N'-diethylmonothiocarbazate; N,N'-diphenylmonothiocarbazat- e;
N,N'-dibenzylmonothiocarbazate;
N,N'-di(pentafluorophenyl)monothiocarba- zate;
N,N'-dicyclohexylmonothiocarbazate; and
N,N'-dinorbornylmonothiocarb- azate.
[0623] S--O Valence Stabilizer #35: Examples of mercapto alcohols
and silylmercaptoalcohols, bis(mercapto alcohols and
silylmercaptoalcohols), and poly(mercapto alcohols and
silylmercaptoalcohols) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-mercaptoethanol (mel); 3-mercaptopropanol (mpl);
2-mercaptophenol; 2-mercaptocyclohexanol; 3-mercapto-2-norborneol;
2-mercaptopyridine]-oxide; 1,4-thioxane; thiodialkanols;
2-(trimethoxysilyl)-1-ethanethiol (tmset);
3-(trimethoxysilyl)-1-propanethiol (tmspt); o-hydroxythiophenols;
o-(O-hydroxyalkyl(aryl))thiophenols; and
o-(S-thioalkyl(aryl))phenols.
[0624] S--O Valence Stabilizer #36: Examples of monothiocarbimates,
bis(monothiocarbimates), and poly(monothiocarbimates) (S--O
Bidentates, S--O Tridentates, and S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
methylmonothiocarbimate; trifluoromethylmonothiocarbimate;
ethylmonothiocarbimate; propylmonothiocarbimate;
isopropylmonothiocarbimate; butylmonothiocarbimate;
tertbutylmonothiocarbimate; cyanomonothiocarbimate;
cyanamidomonothiocarbimate; azidomonothiocarbimate;
phenylmonothiocarbimate; pentafluorophenylmonothi- ocarbimate;
benzylmonothiocarbimate; naphthylmonothiocarbimate;
cyclohexylmonothiocarbimate; norbornylmonothiocarbimate; and
adamantylmonothiocarbimate. [Note: Carbimates tend to stabilize
lower oxidation states in metal ions.]
[0625] S--O Valence Stabilizer #37: Examples of alkyl- and
aryl-monothioborates and bis(monothioborates) (S--O Bidentates and
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: O,O'-diethyl monothioborate;
O,O'-diisopropyl monothioborate; O,O'-diphenyl monothioborate;
O,O'-dibenzyl monothioborate; O,O'-dicyclohexyl monothioborate; and
O,O'-dinorbornyl monothioborate.
[0626] S--O Valence Stabilizer #38: Examples of alkyl- and
aryl-monothioboronates and bis(monothioboronates) (S--O Bidentates
and S--O Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: diethyl monothioboronate;
diisopropyl monothioboronate; diphenyl monothioboronate; dibenzyl
monothioboronate; dicyclohexyl monothioboronate; and dinorbornyl
monothioboronate. [Note: boronates tend to stabilize lower
oxidation states in metal ions.]
[0627] S--O Valence Stabilizer #39: Examples of monothioarsonic
acids (arsonothioic acids), bis(monothioarsonic acids),
poly(monothioarsonic acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
monothioarsonic acid, O-phenylmonothioarsonic acid,
O-benzylmonothioarsonic acid, O-cyclohexylmonothioarsonic acid,
O-norbornylmonothioarsonic acid, O,O-diphenylmonothioarsonic acid,
O,O-dibenzylmonothioarsonic acid, O,O-dicyclohexylmonothioarsonic
acid, and O,O-dinorbornylmonothioarsonic acid.
[0628] S--O Valence Stabilizer #40: Examples of heterocyclic rings
containing one or two sulfur atoms and having at least one
additional oxygen atom binding site not in a ring (S--O Bidentates,
S--O Tridentates, S--O Tetradentates, or S--O Hexadentates) that
meet the requirements for use as narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2-thiopheneethanol (2-(2-thienyl)ethanol); 2-propionylthiophene
(1-(2-thienyl)-1-propanone); N,N'-thiobisphthalimide;
1,1'-thiocarbonyldi-2-pyridone; 2-thiopheneacetic acid;
2-thiophenecarboxaldehyde; 2-thiophenecarboxamide;
2-thiophenecarboxylic acid; 2,5-thiophenedicarboxaldehyde;
2,5-thiophenedicarboxylic acid; 2-thiophenemethanol; 2-thiophenone;
thiotetronic acid; alkyl(aryl) 2-thienyl ketones; dithienyl ketone;
1,3-dithiane-2-carboxylic acid; and 1,3-dithiolane-2-carboxylic
acid.
[0629] S--O Valence Stabilizer #41: Examples of heterocyclic rings
containing one or two oxygen atoms and having at least
one-additional sulfur atom binding site not in a ring (S--O
Bidentates, S--O Tridentates, S--O Tetradentates, or S--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-furanethanethiol (2-(2-furyl)thanethiol);
1-(2-furyl)-1-propanethione); 2-furanthioacetic acid;
2-furanthiocarboxaldehyde; 2-furanthiocarboxamide;
2-furanthiocarboxylic acid; 2,5-furandithiocarboxaldehyde;
2,5-furandithiocarboxylic acid; 2-furanmethanethiol; 2-furanthione;
furfuryl disulfide; furfuryl mercaptan; furfuryl sulfide; and
furfuryl methyl disulfide.
[0630] S--O Valence Stabilizer #42: Examples of heterocyclic rings
containing one or two sulfur atoms and having at least one
additional oxygen atom binding site in a separate ring (S--O
Bidentates, S--O Tridentates, S--O Tetradentates, or S--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-(2-furyl)thiophene; 2,5-(2-furyl)thiophene;
2-(2-furyl)thiopyran; and 2,5-(2-furyl)thiopyran.
[0631] S--O Valence Stabilizer #43: Examples of two-, three-,
four-, five-, six-, seven-, eight-, nine-, and ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur (usually thiol, mercapto, or
thiocarbonyl groups) or oxygen (hydroxy, carboxy, or carbonyl
groups) and are not contained in component heterocyclic rings (S--O
Bidentates, S--O Tridentates, S--O Tetradentates, and S--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: thiaoxacyclobutane ([4]aneOS); thiaoxacyclopentane
([5]aneOS); thiaoxacyclohexane ([6]aneOS); thiaoxacycloheptane
([7]aneOS); thiaoxacyclooctane ([8]aneOS); thiaoxacyclobutene
([4]eneOS); thiaoxacyclopentene ([5]eneOS); thiaoxacyclohexene
([6]eneOS); thiaoxacycloheptene ([7]eneOS); thiaoxacyclooctene
([8]eneOS); dithiaoxacyclohexane ([6]aneOS.sub.2);
dithiaoxacycloheptane ([7]aneOS.sub.2); dithiaoxacyclooctane
([8]aneOS.sub.2); dithiaoxacyclononane ([9]aneOS.sub.2);
dithiaoxacyclodecane ([10]aneOS.sub.2); dithiaoxacycloundecane
([1]aneOS.sub.2); dithiaoxacyclododecane ([12]aneOS.sub.2);
dithiaoxacyclohexene ([6]eneOS.sub.2); dithiaoxacycloheptene
([7]eneOS.sub.2); dithiaoxacyclooctene ([8]encOS.sub.2);
dithiaoxacyclononene ([9]eneOS.sub.2); dithiaoxacyclodecene
([10]eneOS.sub.2); dithiaoxacycloundecene ([11]eneOS.sub.2);
dithiaoxacyclododecene ([12]eneOS.sub.2); dithiadioxacyclooctane
([8]aneO.sub.2S.sub.2); dithiadioxacyclononane
([9]aneO.sub.2S.sub.2); dithiadioxacyclodecane
([10]aneO.sub.2S.sub.2); dithiadioxacycloundecane
([11]aneO.sub.2S.sub.2); dithiadioxacyclododecane
([12]aneO.sub.2S.sub.2)- ; dithiadioxacyclotridecane
([13]aneO.sub.2S.sub.2); dithiadioxacyclotetradecane
([14]aneO.sub.2S.sub.2); dithiadioxacyclopentadecane
([15]aneO.sub.2S.sub.2); dithiadioxacyclohexadecane
([16]aneO.sub.2S.sub.2); dithiadioxacycloheptadecane
([17]aneO.sub.2S.sub.2); dithiadioxacyclooctadecane
([18]aneO.sub.2S.sub.2); dithiadioxacyclononadecane
([19]aneO.sub.2S.sub.2); dithiadioxacycloeicosane
([20]aneO.sub.2S.sub.2); dithiadioxacyclooctadie- ne
([8]dieneO.sub.2S.sub.2); dithiadioxacyclononadiene
([9]dieneO.sub.2S.sub.2); dithiadioxacyclodecadiene
([10]dieneO.sub.2S.sub.2); dithiadioxacycloundecadiene
([11]dieneO.sub.2S.sub.2); dithiadioxacyclododecadiene
([12]dieneO.sub.2S.sub.2); dithiadioxacyclotridecadiene
([13]dieneO.sub.2S.sub.2); dithiadioxacyclotetradecadiene
([14]dieneO.sub.2S.sub.2); dithiadioxacyclopentadecadiene
([15]dieneO.sub.2S.sub.2); dithiadioxacyclohexadecadiene
([16]dieneO.sub.2S.sub.2); dithiadioxacycloheptadecadiene
([17]dieneO.sub.2S.sub.2); dithiadioxacyclooctadecadiene
([18]dieneO.sub.2S.sub.2); dithiadioxacyclononadecadiene
([19]dieneO.sub.2S.sub.2); and dithiadioxacycloeicosadiene
([20]dieneO.sub.2S.sub.2).
[0632] S--O Valence Stabilizer #44: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur or oxygen and are contained in component
heterocyclic rings (S--O Tridentates, S--O Tetradentates, or S--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: difurandithiophenes; difurantrithiophenes;
trifurantritbiophenes; and tetrafurantetratbiophene- s.
[0633] S--O Valence Stabilizer #45: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur or oxygen and are contained in a combination
of heterocyclic rings and thiol, mercapto, thiocarbonyl, hydroxy,
carboxy, and carbonyl groups (S--O Tridentates, S--O Tetradentates,
or S--O Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dithiadifurandithiophen- es;
tetrathiadifurandithiophenes; trithiatrifurantrithiophenes;
trithiatrifurantrithiophenes; tetrathiatetrafurantetrathiophenes;
and octathiatetrafurantetrathiophenes.
[0634] S--O Valence Stabilizer #46: Examples of sulfoxides that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dimethylsulfoxide (DMSO); diethylsulfoxide; diphenylsulfoxide; and
tetrahydrothiophene oxide.
[0635] S--O Valence Stabilizer #47: Examples of sulfones that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
dimethyl sulfone; diethyl sulfone; and diphenyl sulfone.
[0636] S--O Valence Stabilizer #48: Examples of sulfur dioxide
ligands that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: sulfur dioxide (--SO.sub.2) ligands. [Note: Sulfur
dioxide is a reducing agent, and complexed metal ions therefore
tend to prefer lower oxidation states.]
[0637] N--P Valence Stabilizer #1: Examples of aminoaryl phosphines
and iminoaryl phosphines (N--P Bidentates, N--P Tridentates, and
N--P Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: tri(2-aminophenyl)phosphine;
tri(2-aminophenyl)phosphine oxide; and tri(2-aminopbenyl)phosphine
sulfide.
[0638] N--P Valence Stabilizer #2: Examples of heterocyclic rings
containing one, two, three, or four nitrogen atoms and having at
least one additional phosphorus atom binding site not in a ring
(N--P Bidentates, N--P Tridentates, N--P Tetradentates, or N--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tri(2-imidazolyl)phosphine;
tri(2-pyrrolyl)phosphine; tri(2-pyridyl)phosphine;
tri(2-imidazolyl)phosphine oxide; tri(2-pyrrolyl)phosphine oxide;
tri(2-pyridyl)phosphine oxide; tri(2-imidazolyl)phosphine sulfide;
tri(2-pyrrolyl)phosphine sulfide; and tri(2-pyridyl)phosphine
sulfide.
[0639] N--P Valence Stabilizer #3: Examples of heterocyclic rings
containing one, two, or three phosphorus atoms and having at least
one additional nitrogen atom binding site not in a ring (N--P
Bidentates, N--P Tridentates, N--P Tetradentates, or N--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-aminophosphole; 2,5-diaminophosphole;
2-(aminomethyl)phosphole; 2,5-di(aminomethyl)phosph- ole;
2-aminophosphorin; 2,6-diaminophosphorin;
2-(aminomethyl)phosphorin; 2,6-di(aminomethyl)phosphorin;
triaminocyclotriphosphazenes; and hexaminocyclotriphosphazenes.
[0640] N--P Valence Stabilizer #4: Examples of heterocyclic rings
containing one, two, three, or four nitrogen atoms and having at
least one additional phosphorus atom binding site in a separate
ring (N--P Bidentates, N--P Tridentates, N--P Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2-(2-pyrrolyl)phosphole- ; 2,5-di(2-pyrrolyl)phosphole;
2-(2-pyridyl)phosphorin; and 2,6-(2-pyridyl)phosphorin.
[0641] N--P Valence Stabilizer #5: Examples of two-, three-, four-,
five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) or
phosphorus and are not contained in component heterocyclic rings
(N--P Bidentates, N--P Tridentates, N--P Tetradentates, and N--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: cyclobiphosphazenes; cyclotriphosphazenes;
cyclotetraphosphazenes; cyclopentaphosphazenes;
cyclohexaphosphazenes; diphosphatetraazacyclooctatetraenes;
diphospha-s-triazines; and phospha-s-triazines.
[0642] N--P Valence Stabilizer #6: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen or phosphorus and are contained in
component heterocyclic rings (N--P Bidentates, N--P Tridentates,
N--P Tetradentates, or N--P Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diphospholedipyrroles; diphosphorindipyridines;
triphospholetripyrroles; triphosphorintripyridines;
tetraphospholetetrapyrroles; and tetraphosphorintetrapyridines.
[0643] N--P V alence Stabilizer #7: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen or phosphorus and are contained in a
combination of heterocyclic rings and amine, imine, and phosphine
groups (N--P Bidentates, N--P Tridentates, N--P Tetradentates, or
N--P Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: azaphosphatetraphyrins;
diazadiphosphatetraphyrins; azaphosphahexaphyrins;
diazadiphosphahexaphyrins; triazatriphosphahexaphyrins; and
apholate.
[0644] S--P Valence Stabilizer #1: Examples of thioaryl phosphines
(S--P Bidentates, S--P Tridentates, S--P Tetradentates, and S--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tri(2-mercaptophenyl)phosphine;
tri(2-mercaptophenyl)phosphine oxide; and
tri(2-inercaptophenyl)phosphine sulfide.
[0645] S--P Valence Stabilizer #2: Examples of heterocyclic rings
containing one or two sulfur atoms and having at least one
additional phosphorus atom binding site not in a ring (S--P
Bidentates, S--P Tridentates, S--P Tetradentates, or S--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tri(2-thiophene)phosphi- ne;
tri(2-thiopyran)phosphine; tri(2-thiophene)phosphine oxide;
tri(2-thiopyran)phosphine oxide; tri(2-thiophene)phosphine sulfide;
and tri(2-thiopyran)phosphine sulfide.
[0646] S--P Valence Stabilizer #3: Examples of heterocyclic rings
containing one, two, or three phosphorus atoms and having at least
one additional sulfur atom binding site not in a ring (S--P
Bidentates, S--P Tridentates, S--P Tetradentates, or S--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-mercaptophosphole; 2,5-dimercaptophosphole;
2-(mercaptomethyl)phosphole; 2,5-di(mercaptomethyl)phosphole;
2-mercaptophosphorin; 2,6-dimercaptophosphorin;
2-(mercaptomethyl)phosphorin; and
2,6-di(mercaptomethyl)phosphorin.
[0647] S--P Valence Stabilizer #4: Examples of heterocyclic rings
containing one or two sulfur atoms and having at least one
additional phosphorus atom binding site in a separate ring (S--P
Bidentates, S--P Tridentates, S--P Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2-(2-thienyl)phosphole; 2,5-di(2-thienyl)phosphol- e;
2-(2-thienyl)phosphorin; and 2,6-(2-thienyl)phosphorin.
[0648] S--P Valence Stabilizer #5: Examples of two-, three-, four-,
five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol, mercapto, or thiocarbonyl
groups) or phosphorus and are not contained in component
heterocyclic rings (S--P Bidentates, S--P Tridentates, S--P
Tetradentates, and S--P Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: phosphathiacyclobutane
([4]anePS); phosphathiacyclopentane ([5]anePS);
phosphathiacyclohexane ([6]anePS); phosphathiacycloheptane
([7]anePS); phosphathiacyclooctane ([8]anePS);
diphospbathiacyclohexane ([6]aneSP.sub.2);
diphosphathiacycloheptane ([7]aneSP.sub.2);
diphosphathiacyclooctane ([8]aneSP.sub.2); diphosphathiacyclononane
([9]aneSP.sub.2); diphosphathiacyclodecane ([10]aneSP.sub.2);
diphosphathiacycloundecane ([11]aneSP.sub.2);
diphosphathiacyclododecane ([12]aneSP.sub.2);
diphosphadithiacyclooctane ([8]aneS.sub.2P.sub.2);
diphosphadithiacyclononane ([9]aneS.sub.2P.sub.2);
diphosphadithiacyclodecane ([10] aneS.sub.2P.sub.2);
diphospbadithiacycloundecane ([11]aneS.sub.2P.sub.2);
diphosphadithiacyclododecane ([12]aneS.sub.2P.sub.2);
diphosphadithiacyclotridecane ([13]aneS.sub.2P.sub.2);
diphosphadithiacyclotetradecane ([14]aneS.sub.2P.sub.2);
diphosphadithiacyclopentadecane ([15]aneS.sub.2P.sub.2);
diphosphadithiacyclohexadecane ([16]aneS.sub.2P.sub.2);
diphosphadithiacycloheptadecane ([17]aneS.sub.2P.sub.2);
diphosphadithiacyclooctadecane ([18]aneS.sub.2P.sub.2);
diphosphadithiacyclononadecane ([19]aneS.sub.2P.sub.2);
diphosphadithiacycloeicosane ([20]aneS.sub.2P.sub.2).
[0649] S--P Valence Stabilizer #6: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur or phosphorus and are contained in component
heterocyclic rings (S--P Bidentates, S--P Tridentates, S--P
Tetradentates, or S--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diphospholedithiophenes;
diphosphorindithiopyrans; triphospholetrithiophenes;
triphosphorintrithiopyrans; tetraphospholetetrathiophenes; and
tetraphosphorintetrathiopyrans.
[0650] S--P Valence Stabilizer #7: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur or phosphorus and are contained in a
combination of heterocyclic rings and thiol, mercapto,
thiocarbonyl, and phosphine groups (S--P Bidentates, S--P
Tridentates, S--P Tetradentates, or S--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
thiaphosphatetraphyrins- ; dithiadiphosphatetraphyrins;
thiaphosphahexaphyrins; dithiadiphosphahexaphyrins; and
trithiatriphosphahexaphyrins.
[0651] P--O Valence Stabilizer #1: Examples of hydroxyaryl
phosphines (P--O Bidentates, P--O Tridentates, P--O Tetradentates,
and P--O Hexadentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: tri(2-hydroxyphenyl)phosphine;
tri(2-hydroxyphenyl)phosphine oxide; and
tri(2-hydroxyphenyl)phosphine sulfide.
[0652] P--O Valence Stabilizer #2: Examples of heterocyclic rings
containing one or two oxygen atoms and having at least one
additional phosphorus atom binding site not in a ring (P--O
Bidentates, P--O Tridentates, P--O Tetradentates, or P--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: tri(2-furan)phosphine; tri(2-pyran)phosphine;
tri(2-furan)phosphine oxide; tri(2-pyran)phosphine oxide;
tri(2-furan)phosphine sulfide; and tri(2-pyran)phosphine
sulfide.
[0653] P--O Valence Stabilizer #3: Examples of heterocyclic rings
containing one, two, or three phosphorus atoms and having at least
one additional oxygen atom binding site not in a ring (P--O
Bidentates, P--O Tridentates, P--O Tetradentates, or P--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2-hydroxyphosphole; 2,5-dihydroxyphosphole;
2-(hydroxymethyl)phosphole; 2,5-di(hydroxymethyl)phosphole;
2-hydroxyphosphorin; 2,6-dihydroxyphosphorin;
2-(hydroxymethyl)phosphorin; and
2,6-di(hydroxymethyl)phosphorin.
[0654] P--O Valence Stabilizer #4: Examples of heterocyclic rings
containing one or two oxygen atoms and having at least one
additional phosphorus atom binding site in a separate ring (P--O
Bidentates, P--O Tridentates, P--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2-(2-furyl)phosphole; 2,5-di(2-furyl)phosphole;
2-(2-furyl)phosphorin; and 2,6-(2-furyl)phosphorin.
[0655] P--O Valence Stabilizer #5: Examples of two-, three-, four-,
five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of oxygen (usually hydroxy, carboxy, or carbonyl
groups) or phosphorus and are not contained in component
heterocyclic rings (P--O Bidentates, P--O Tridentates, P--O
Tetradentates, and P--O Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: phosphaoxacyclobutane
([4]anePO); phosphaoxacyclopentane ([5]anePO);
phosphaoxacyclohexane ([6]anePO); phosphaoxacycloheptane
([7]anePO); phosphaoxacyclooctane ([8]anePO);
diphosphaoxacyclohexane ([6]aneOP.sub.2); diphosphaoxacycloheptane
([7]aneOP.sub.2); diphosphaoxacyclooctane ([8]aneOP.sub.2);
diphosphaoxacyclononane ([9]aneOP.sub.2); diphosphaoxacyclodecane
([10]aneOP.sub.2); diphosphaoxacycloundecane ([11]aneOP.sub.2);
diphosphaoxacyclododecane ([12]aneOP.sub.2);
diphosphadioxacyclooctane ([8]aneO.sub.2P.sub.2);
diphosphadioxacyclonona- ne ([9]aneO.sub.2P.sub.2);
diphosphadioxacyclodecane ([10]aneO.sub.2P.sub.2);
diphosphadioxacycloundecane ([1]aneO.sub.2P.sub.2);
diphosphadioxacyclododecane ([12]aneO.sub.2P.sub.2);
diphosphadioxacyclotridecane ([13]aneO.sub.2P.sub.2);
diphosphadioxacyclotetradecane ([14]aneO.sub.2P.sub.2);
diphosphadioxacyclopentadecane ([15]aneO.sub.2P.sub.2);
diphosphadioxacyclohexadecane ([16]aneO.sub.2P.sub.2);
diphosphadioxacycloheptadecane ([17]aneO.sub.2P.sub.2);
diphosphadioxacyclooctadecane ([18]aneO.sub.2P.sub.2);
diphosphadioxacyclononadecane ([19]aneO.sub.2P.sub.2);
diphosphadioxacycloeicosane ([20]aneO.sub.2P.sub.2); and
dioxaphospholane.
[0656] P--O Valence Stabilizer #6: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of oxygen or phosphorus and are contained in component
heterocyclic rings (P--O Bidentates, P--O Tridentates, P--O
Tetradentates, or P--O Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: diphospholedifurans;
diphosphorindipyrans; triphospholetrifurans;
triphosphorintripyrans; tetraphospholetetrafurans; and
tetraphosphorintetrapyrans.
[0657] P--O Valence Stabilizer #7: Examples of four-, five-, six-,
seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of oxygen or phosphorus and are contained in a
combination of heterocyclic rings and hydroxy, carboxy, caibonyl,
and phosphine groups (P--O Bidentates, P--O Tridentates, P--O
Tetradentates, or P--O Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: oxaphosphatetraphyrins;
dioxadiphosphatetraphyrins; oxaphosphahexaphyrins;
dioxadiphosphahexaphyrins; and trioxatriphosphahexaphyrins.
[0658] As Valence Stabilizer #1: Examples of monoarsines (As
Monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: arsine, triphenylarsine, ticyclohexylarsine,
methyldiphenylarsine, ethyldiphenylarsine, arsinonorbornane, and
arsinoadamantane.
[0659] As Valence Stabilizer #2: Examples of diarsines (As
Monodentates or As--As Bidentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
bis(diphenylarsino)methane, bis(diphenylarsino)ethane,
bis(diphenylarsino)propane, bis(diphenylarsino)butane,
bis(diphenylarsino)pentane, 1,2-diarsinobenzene,
cyclohexane-1,2-diarsine- , 1,2-bis(phenylbutylarsino)ethane,
o-phenylenebis(methylphenylarsine) and
o-phenylenebis(dimethylarsine) (diars). (Note: the aryl derivatives
are air-stable, whereas the alkyl derivatives are air-sensitive and
therefore unsuitable for these applications.)
[0660] As Valence Stabilizer #3: Examples of triarsines (As--As
Bidentates, or As--As Tridentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
1,1,5,9,9-pentaphenyl-1,5,9-triarsanonane,
3-methyl-3-(As,As-dimethyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapen-
tane, As,As-[o-(As-dimethyl)arsinodiphenyl]-(As-phenyl)arsine,
As,As-[o-(As-diphenyl)arsinodiphenyl]-(As-phenyl)arsine,
hexahydro-2,4,6-trimethyl-1,3,5-triarsinazine. (Note: the aryl
derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.)
[0661] As Valence Stabilizer #4: Examples of tetraarsines (As--As
Bidentates, As--As Tridentates, or As--As Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
3,3-(As-diphenyl)arsino-
methyl-1,1,5,5-tetraphenyl-1,5-diarsapentane. (Note: the aryl
derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.)
[0662] As Valence Stabilizer #5: Examples of pentaarsines (As--As
Bidentates, As--As Tridentates, or As--As Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
4-[2-(As-diphenyl)arsin-
oethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraarsadecane. (Note:
the aryl derivatives are air-stable, whereas the alkyl derivatives
are air-sensitive and therefore unsuitable for these
applications.)
[0663] As Valence Stabilizer #6: Examples of hexaarsines (As--As
Bidentates, As--As Tridentates, As--As Tetradentates, or As--As
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to:
o-phenylenebis[di-3-(As-diphenyl)arsinopropylarsine]. (Note: the
aryl derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.)
[0664] As Valence Stabilizer #7: Examples of 5-membered
heterocyclic rings containing one arsenic atom (As Monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: arsole, azarsole, diazarsole, benzarsole, benzazarsole,
dibenzarsole, naphtharsole, naphthazarsole.
[0665] As Valence Stabilizer #8: Examples of 6-membered
heterocyclic rings containing one arsenic atom (As Monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: arsenin, azarsenin, diazarsenin, benzarsenin,
benzazarsenin, dibenzarsenin, naphtharsenin, and
naphthazarsenin.
[0666] As Valence Stabilizer #9: Examples of 5-membered
heterocyclic rings containing one arsenic atom and having at least
one additional arsenic atom binding site not contained in a ring
(As Monodentates, As--As Bidentates, As--As Tridentates, As--As
Tetradentates, or As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(As-phenylarsino)arsole; 2,5-(As-phenylarsino)arsole;
2-(As-phenylarsino)benzarsole; 7-(As-phenylarsino)benzarsole; and
1,8-(As-phenylarsino)dibenzarsole.
[0667] As Valence Stabilizer #10: Examples of 6-membered
heterocyclic rings containing one arsenic atom and having at least
one additional arsenic atom binding site not contained in a ring
(As Monodentates, As--As Bidentates, As--As Tridentates, As--As
Tetradentates, or As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2-(As-phenylarsino)arsenin; 2,5-(As-phenylarsino)arsenin;
2-(As-phenylarsino)benzarsenin; 7-(As-phenylarsino)benzarsenin; and
1,9-(As-phenylarsino)dibenzarsenin.
[0668] As Valence Stabilizer #11: Examples of 5-membered
heterocyclic rings containing one arsenic atom and having at least
one additional arsenic atom binding site contained in a ring (As
Monodentates, As--As Bidentates, As--As Tridentates, As--As
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-biarsole; 2,2',2"-triarsole; and
2,2'-bibenzarsole.
[0669] As Valence Stabilizer #12: Examples of 6-membered
heterocyclic rings containing one arsenic atom and having at least
one additional arsenic atom binding site contained in a ring (As
Monodentates, As--As Bidentates, As--As Tridentates, As--As
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-biarsenin; 2,2',2"-triarsenin;
2,2',2",2'"-tetraarsenin; 2,2'-bibenzarsenin; and
8,8'-bibenzarsenin.
[0670] As Valence Stabilizer #13a: Examples of two-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein both
binding sites are composed of arsenic and are not contained in
component heterocyclic rings (As--As Bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
As,As-diphenyldiarsacyclobutane ([4]aneAs.sub.2);
As,As-diphenyldiarsacyclopentane ([5]aneAs.sub.2);
As,As-diphenyldiarsacyclohexane ([6]aneAs.sub.2);
As,As-diphenyldiarsacyc- loheptane ([7]aneAs.sub.2);
As,As-diphenyldiarsacyclooctane ([8]aneAs.sub.2);
As,As-diphenyldiarsacyclobutene ([4]eneAs.sub.2);
As,As-diphenyldiarsacyclopentene ([5]eneAs.sub.2);
As,As-diphenyldiarsacyclohexene ([6]eneAs.sub.2);
As,As-diphenyldiarsacyc- loheptene ([7]eneAs.sub.2); and
As,As-diphenyldiarsacyclooctene ([8]eneAs.sub.2).
[0671] As Valence Stabilizer #13b: Examples of three-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of arsenic and are not contained in
component heterocyclic rings (As--As Tridentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
As,As,As-triphenyltriarsacyclohexane ([6]aneAs.sub.3);
As,As,As-triphenyltriarsacycloheptane ([7]aneAs.sub.3);
As,As,As-triphenyltriarsacyclooctane ([8]aneAs.sub.3);
As,As,As-triphenyltriarsacyclononane ([9]aneAs.sub.3);
As,As,As-triphenyltriarsacyclodecane ([10]aneAs.sub.3);
As,As,As-triphenyltriarsacycloundecane ([11]aneAs.sub.3);
As,As,As-triphenyltriarsacyclododecane ([12]aneAs.sub.3);
As,As,As-triphenyltriarsacyclohexatriene ([6]trieneAs.sub.3);
As,As,As-triphenyltriarsacycloheptatriene ([7]trieneAs.sub.3);
As,As,As-triphenyltriarsacyclooctatriene ([8]trieneAs.sub.3);
As,As,As-triphenyltriarsacyclononatriene ([9]trieneAs.sub.3);
As,As,As-triphenyltriarsacyclodecatriene ([10]trieneAs.sub.3);
As,As,As-triphenyltriarsacycloundecatriene ([11]trieneAs.sub.3);
and As,As,As-triphenyltriarsacyclododecatriene
([12]trieneAs.sub.3).
[0672] As Valence Stabilizer #13c: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of arsenic and are not contained in
component heterocyclic rings (As--As Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
As,As,As,As-tetraphenyltetraarsacyclooctane ([8]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclononane ([9]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclodecane ([10]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacycloundecane ([11]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclododecane ([12]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclotridecane ([13]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclotetradecane ([14]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclopentadecane ([15]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclohexadecane ([16]aneAs.sub.4);
As,As,As,As,As-etraphenyltetraarsacycloheptadecane
([17]aneAs.sub.4); As,As,As,As-etraphenyltetraarsacyclooctadecane
([18]aneAs.sub.4); As,As,As,As-etraphenyltetraarsacyclononadecane
([19]aneAs.sub.4); and
As,As,As,As-tetraphenyltetraarsacycloeicosane
([20]aneAs.sub.4).
[0673] As Valence Stabilizer #13d: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of arsenic and are not contained in
component heterocyclic rings (As--As Tridentates, As--As
Tetradentates, or As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: As,As,As,As,As,As-hexap-
henylhexaarsacyclododecane ([12]aneAs.sub.6);
As--As,As,As,As,As-hexapheny- lhexaarsacyclotridecane
([13]aneAs.sub.6); As,As,As,As,As,As-hexaphenylhex-
aarsacyclotetradecane ([14]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaa- rsacyclopentadecane
([15]aneAs.sub.6); As,As,As,As,As,As-hexaphenylhexaars-
acyclohexadecane ([16]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacy- cloheptadecane
([17]aneAs.sub.6); As,As,As,As,As,As-hexaphenylhexaarsacycl-
ooctadecane ([18]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclono- nadecane
([19]aneAs.sub.6); As,As,As,As,As,As-hexaphenylhexaarsacycloeicos-
ane ([20]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacycloheneicosan- e
([21]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclodocosane
([22]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclotricosane
([23]aneAs.sub.6); and
As,As,As,As,As,As-hexaphenylhexaarsacyclotetracosa- ne
([24]aneAs.sub.6).
[0674] As Valence Stabilizer #14a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of arsenic and are contained in
component 5-membered heterocyclic rings (As--As Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetraarsoles.
[0675] As Valence Stabilizer #14b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of arsenic and are contained in
component 5-membered heterocyclic rings (As--As Tetradentates and
As--As Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: hexaarsoles.
[0676] As Valence Stabilizer #15a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of arsenic and are contained in a
combination of 5-membered heterocyclic rings and arsine groups
(As--As Tridentates, As--As Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diarsatetraarsoles; and tetraarsatetraarsoles.
[0677] As Valence Stabilizer #15b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of arsenic and are contained in a
combination of 5-membered heterocyclic rings and phosphine groups
(As--As Tridentates, As--As Tetradentates, and As--As Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diarsahexaarsoles; and triarsahexaarsoles.
[0678] As Valence Stabilizer #16a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of arsenic and are contained in
component 6-membered heterocyclic rings (As--As Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
cyclotetraarsenins.
[0679] As Valence Stabilizer #16b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of arsenic and are contained in
component 6-membered heterocyclic rings (As--As Tridentates, As--As
Tetradentates, and As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to: cyclohexaarsenins.
[0680] As Valence Stabilizer #17a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of arsenic and are contained in a
combination of 6-membered heterocyclic rings and arsine groups
(As--As Tridentates, As--As Tetradentates, or As--As Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diarsacyclotetraarsenins; and
tetraarsacyclotetraarsenins.
[0681] As Valence Stabilizer #17b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of arsenic and are contained in a
combination of 6-membered heterocyclic rings and arsine groups
(As--As Tridentates, As--As Tetradentates, or As--As Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: diarsacyclohexaarsenins; and
triarsacyclohexaarsenins.
[0682] Se Valence Stabilizer #1: Examples of monoselenoethers (Se
Monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hydrogen selenide, dimethyl selenide, diethyl
selenide, dioctyl selenide, diphenyl selenide, dicyclohexyl
selenide, tetramethylene selenide, trimethylene selenide,
dimethylene selenide, and selenobicycloheptane.
[0683] Se Valence Stabilizer #2: Examples of diselenoethers (Se
Bidentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,5-dimethyl-3,6-diselenaoctane;
2,5-diselenahexane; 2,6-diselenaheptane; 3,7-diselenanonane;
3,6-diselenaoctane; 3-butenyl butyl selenoether (bbs); 4-pentenyl
butyl selenoether (pbs); 3-butenyl phenyl selenoether (bps); and
4-pentenyl phenyl selenoether (pps).
[0684] Se Valence Stabilizer #3: Examples of triselenoethers (Se
Bidentates or Se Tridentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: 1,3,5-triselenane;
2,5,8-triselenanonane; 3,6,9-triselenaundecane; and
2,6,10-triselenaundecane.
[0685] Se Valence Stabilizer #4: Examples of tetraselenoethers (Se
Bidentates, Se Tridentates, or Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
2,6,10,14-tetraselenape- ntadecane and
2,5,8,11-tetraselenadodecane.
[0686] Se Valence Stabilizer #5a: Examples of 5-membered
heterocyclic rings containing one selenium atom (Se Monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: dihydroselenophene, selenophene, selenazole,
selenapyrroline, selenaphospholene, selenaphosphole, oxaselenole,
selenadiazole, selenatriazole, benzodihydroselenophene,
benzoselenophene, benzoselenazole, benzoselenaphosphole,
dibenzoselenophene, and naphthoselenophene.
[0687] Se Valence Stabilizer #5b: Examples of 5-membered
heterocyclic rings containing two selenium atoms (Se Monodentates
or Se Bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: diselenole, benzodiselenole, and
naphthodiselenole.
[0688] Se Valence Stabilizer #6a: Examples of 6-membered
heterocyclic rings containing one selenium atom (Se Monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: dihydroselenopyran, selenopyran, selenazine,
selenadiazine, selenaphosphorin, selenadiphosphorin, oxaselenin,
benzoselenopyran, dibenzoselenopyran, and naphthoselenopyran.
[0689] Se Valence Stabilizer #6b: Examples of 6-membered
heterocyclic rings containing two selenium atoms (Se Monodentates
or Se Bidentates)that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: dihydrodiselenin, diselenin,
benzodiselenin, dibenzodiselenin, and naphthodiselenin.
[0690] Se Valence Stabilizer #7: Examples of 5-membered
heterocyclic rings containing one selenium atom and having at least
one additional selenium atom binding site not contained in a ring
(Se Monodentates, Se--Se Bidentates, Se--Se Tridentates, Se--Se
Tetradentates, or Se--Se Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,5-diseleno-2,5-dihydroselenophene;
2,5-bis(selenomethyl)-2,5-dihydr- oselenophene;
2,5-bis(2-selenophenyl)-2,5-dihydroselenophene;
2,5-diseleno(selenophene); 2,5-bis(selenomethyl)selenophene;
2,5-bis(2-selenophenyl)selenophene; 2,5-diseleno(selenazole);
2,5-bis(selenomethyl)selenazole; 2,5-bis(2-selenophenyl)selenazole;
and 2,5-diseleno-1,3,4-selenadiazole [bismuthselenol].
[0691] Se Valence Stabilizer #8: Examples of 6-membered
heterocyclic rings containing one selenium atom and having at least
one additional selenium atom binding site not contained in a ring
(Se Monodentates, Se--Se Bidentates, Se--Se Tridentates, Se--Se
Tetradentates, or Se--Se Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
2,6-diseleno-2,5-dihydroselenopyran;
2,6-bis(selenomethyl)-2,5-dihydr- oselenopyran;
2,6-bis(2-selenophenyl)-2,5-dihydroselenopyran;
2,6-diseleno(selenopyran); 2,6-bis(selenomethyl)selenopyran;
2,6-bis(2-selenophenyl)selenopyran; 2,6-diseleno(selenazine);
2,6-bis(selenomethyl)selenazine; 2,6-bis(2-selenophenyl)selenazine;
2,6-diseleno-1,3,5-selenadiazine; 2-seleno-1-benzoselenopyran;
8-seleno-1-benzoselenopyran; and
1,9-diselenodibenzoselenopyran.
[0692] Se Valence Stabilizer #9: Examples of 5-membered
heterocyclic rings containing one selenium atom and having at least
one additional selenium atom binding site contained in a ring (Se
Monodentates, Se--Se Bidentates, Se--Se Tridentates, Se--Se
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-2,5-dihydrosele- nophene;
2,2',2"-tri-2,5-dihydroselenophene; 2,2'-biselenophene;
2,2',2"-triselenophene; 2,2'-biselenazole; 5,5'-biselenazole;
2,2'-bi-1,3,4-selenadiazole; 2,2'-biselenanaphthene;
2,2'-bibenzoselenazole; and 1,1'-bis(dibenzoselenophene).
[0693] Se Valence Stabilizer #10: Examples of 6-membered
heterocyclic rings containing one selenium atom and having at least
one additional selenium atom binding site contained in a ring (Se
Monodentates, Se--Se Bidentates, Se--Se Tridentates, Se--Se
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: 2,2'-bi-2,5-dihydrosele- nopyran;
2,2',2"-tri-2,5-dihydroselenopyran; 2,2'-biselenopyran;
2,2',2"-triselenopyran; 2,2'-bi-1,4-selenazine;
2,2'-bi-1,3,5-selenadiazi- ne; 2,2'-bi-1-benzoselenopyran; and
1,1'-bis(dibenzoselenopyran).
[0694] Se Valence Stabilizer #11a: Examples of two-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein both
binding sites are composed of selenium (usually selenol or
selenoether groups) and are not contained in component heterocyclic
rings (Se--Se Bidentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: diselenacyclobutane
([4]aneSe.sub.2); diselenacyclopentane ([5]aneSe.sub.2);
diselenacyclohexane ([6]aneSe.sub.2); diselenacycloheptane
([7]aneSe.sub.2); diselenacyclooctane ([8]aneSe.sub.2);
diselenacyclobutene ([4]eneSe.sub.2); diselenacyclopentene
([5]eneSe.sub.2); diselenacyclohexene ([6]eneSe.sub.2);
diselenacycloheptene ([7]eneSe.sub.2); diselenacyclooctene
([8]eneSe.sub.2); diselenacyclobutadiene ([4]dieneSe.sub.2);
diselenacyclopentadiene ([5]dieneSe.sub.2); diselenacyclohexadiene
([6]dieneSe.sub.2); diselenacycloheptadiene ([7]dieneSe.sub.2); and
diselenacyclooctadiene ([8]dieneSe.sub.2).
[0695] Se Valence Stabilizer #11b: Examples of three-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of selenium (usually selenol or
selenoether groups) and are not contained in component heterocyclic
rings (Se--Se Tridentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: triselenacyclohexane
([6]aneSe.sub.3); triselenacycloheptane ([7]aneSe.sub.3);
triselenacyclooctane ([8]aneSe.sub.3); triselenacyclononane
([9]aneSe.sub.3); triselenacyclodecane ([10]aneSe.sub.3);
triselenacycloundecane ([11]aneSe.sub.3); triselenacyclododecane
([12]aneSe.sub.3); triselenacyclohexene ([6]eneSe.sub.3);
triselenacycloheptene ([7]eneSe3); triselenacyclooctene
([8]eneSe.sub.3); triselenacyclononene ([9]eneSe.sub.3);
triselenacyclodecene ([10]eneSe.sub.3); triselenacycloundecene
([11]eneSe.sub.3); triselenacyclododecene ([12]eneSe.sub.3);
triselenacyclohexatriene ([6]trieneSe.sub.3);
triselenacycloheptatriene ([7]trieneSe.sub.3);
triselenacyclooctatriene ([8]trieneSe.sub.3);
triselenacyclononatriene ([9]trieneSe.sub.3);
triselenacyclodecatriene ([10]trieneSe.sub.3);
triselenacycloundecatriene ([11]trieneSe.sub.3); and
triselenacyclododecatriene ([12]trieneSe.sub.3).
[0696] Se Valence Stabilizer #11c: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of selenium (usually selenol or
selenoether groups) and are not contained in component heterocyclic
rings (Se--Se Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4
include, but are not limited to: tetraselenacyclooctane
([8]aneSe.sub.4); tetraselenacyclononane ([9]aneSe.sub.4);
tetraselenacyclodecane ([10]aneSe.sub.4); tetraselenacycloundecane
([11]aneSe.sub.4); tetraselenacyclododecane ([12]aneSe.sub.4);
tetraselenacyclotridecane ([13]aneSe.sub.4);
tetraselenacyclotetradecane ([14]aneSe.sub.4);
tetraselenacyclopentadecane ([15]aneSe.sub.4);
tetraselenacyclohexadecane ([16]aneSe.sub.4);
tetraselenacycloheptadecane ([17]aneSe.sub.4);
tetraselenacyclooctadecane ([18]aneSe.sub.4);
tetraselenacyclononadecane ([19]aneSe.sub.4);
tetraselenacycloeicosane ([20]aneSe.sub.4);
tetraselenacyclooctadiene ([8]dieneSe.sub.4);
tetraselenacyclononadiene ([9]dieneSe.sub.4);
tetraselenacyclodecadiene ([10]dieneSe.sub.4);
tetraselenacycloundecadiene ([11]dieneSe.sub.4);
tetraselenacyclododecadiene ([12]dieneSe.sub.4);
tetraselenacyclotridecad- iene ([13]dieneSe.sub.4);
tetraselenacyclotetradecadiene ([14]dieneSe.sub.4);
tetraselenacyclopentadecadiene ([15]dieneSe.sub.4);
tetraselenacyclohexadecadiene ([16]dieneSe.sub.4);
tetraselenacycloheptadecadiene ([17]dieneSe.sub.4);
tetraselenacyclooctadecadiene ([18]dieneSe.sub.4);
tetraselenacyclononadecadiene ([19]dieneSe.sub.4);
tetraselenacycloeicosadiene ([20]dieneSe.sub.4);
tetraselenacyclooctatetr- adiene ([8]tetradieneSe.sub.4);
tetraselenacyclononatetradiene ([9]tetradieneSe.sub.4);
tetraselenacyclodecatetradiene ([10]tetradieneSe.sub.4); and
tetraselenacycloundecatetradiene ([11]tetradieneSe.sub.4).
[0697] Se Valence Stabilizer #11d: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of selenium (usually selenol or
selenoether groups) and are not contained in component heterocyclic
rings (Se--Se Tridentates, Se--Se Tetradentates, or Se--Se
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: hexaselenacyclododecane ([12]aneSe.sub.6);
hexaselenacyclotadecane ([13]aneSe.sub.6);
hexaselenacyclotetradecane ([14]aneSe.sub.6);
hexaselenacyclopentadecane ([15]aneSe.sub.6);
hexaselenacyclohexadecane ([16]aneSe.sub.6);
hexaselenacycloheptadecane ([17]aneSe.sub.6);
hexaselenacyclooctadecane ([18]aneSe.sub.6);
hexaselenacyclononadecane ([19]aneSe.sub.6);
hexaselenacycloeicosane ([20]aneSe.sub.6);
hexaselenacycloheneicosane ([21]aneSe.sub.6);
hexaselenacyclodocosane ([22]aneSe.sub.6); hexaselenacyclotricosane
([23]aneSe.sub.6); hexaselenacyclotetracosane ([24]aneSe.sub.6);
hexaselenacyclododecatriene ([12]trieneSe.sub.6);
hexaselenacyclotridecat- riene ([13]trieneSe.sub.6);
hexaselenacyclotetradecatriene ([14]trieneSe.sub.6);
hexaselenacyclopentadecatriene ([15]trieneSe.sub.6);
hexaselenacyclohexadecatriene ([16]trieneSe.sub.6);
hexaselenacycloheptadecatriene ([17]trieneSe.sub.6); and
hexaselenacyclooctadecatriene ([18]trieneSe.sub.6).
[0698] Se Valence Stabilizer #12a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of selenium and are contained in
component 5-membered heterocyclic rings (Se--Se Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetraselenophenes; tetraselenaphospholes; tetraoxaselenoles; and
tetradiselenoles.
[0699] Se Valence Stabilizer #12b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of selenium and are contained in
component 5-membered heterocyclic rings (Se--Se Tridentates or
Se--Se Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: hexaselenophenes; hexaselenaphospholes;
hexaoxaselenoles; and hexadiselenoles.
[0700] Se Valence Stabilizer #13a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of selenium and are contained in a
combination of 5-membered heterocyclic rings and selenol and
selenoether groups (Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diselenatetraselenophenes; tetraselenatetraselenophenes;
diselenatetradiselenoles; and tetraselenatetradiselenoles.
[0701] Se Valence Stabilizer #13b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of selenium and are contained in a
combination of 5-membered heterocyclic rings and selenol or
selenoether groups (Se--Se Tridentates or Se--Se Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diselenahexaselenophenes; and triselenahexaselenophenes.
[0702] Se Valence Stabilizer #14a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of selenium and are contained in
component 6-membered heterocyclic rings (Se--Se Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetraselenopyrans; tetraselenaphosphorins;
tetraselenadiphosphorins; tetraoxaselenins; and
tetradiselenins.
[0703] Se Valence Stabilizer #14b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of selenium and are contained in
component 6-membered heterocyclic rings (Se--Se Tridentates or
Se--Se Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: hexaselenopyrans; hexaselenaphosphorins;
hexaselenadiphosphorins; hexaoxaselenins; and hexadiselenins.
[0704] Se Valence Stabilizer #15a: Examples of four-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
four binding sites are composed of selenium and are contained in a
combination of 6-membered heterocyclic rings and selenol or
selenoether groups (Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diselenatetraselenopyrans; tetraselenatetraselenopyrans;
diselenatetraselenaphosphorins; tetraselenatetraselenaphospborins;
diselenatetraoxaselenins; tetraselenatetraoxaselenins;
diselenatetradiselenins; and tetraselenatetradiselenins.
[0705] Se Valence Stabilizer #15b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of selenium and are contained in a
combination of 6-membered heterocyclic rings and selenol or
selenoether groups (Se--Se Tridentates, Se--Se Tetradentates, or
Se--Se Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include,
but are not limited to: diselenahexaselenopyrans;
triselenahexaselenopyrans; diselenahexaselenaphosphorins;
triselenahexaselenaphosphorins; diselenahexaoxaselenins;
triselenahexaoxaselenins; diselenahexadiselenins; and
triselenahexadiselenins.
[0706] Se Valence Stabilizer #16: Examples of 1,3-diselenoketones
(diseleno-beta-ketonates), 1,3,5-triselenoketones,
bis(1,3-diselenoketones), and poly(1,3-diselenoketones) (Se--Se
Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
hexafluoropentanedisele- none; 1,3-diphenyl-1,3-propanediselenone;
selenobenzoylselenopinacolone; diselenocyclohexoylmethane;
diphenylpentanetriselenoate; tetramethylnonanetriselenoate;
hexafluoroheptanetriselenoate; trifluoroheptanetriselenoate;
1-(2-thienyl)-1,3-butanediselenone,
1-(2-naphthyl)-1,3-butanediselenone, and
trifluoroselenoacetylselenocamph- or.
[0707] Se Valence Stabilizer #17: Examples of 1,1-diselenolates,
bis(1,1-diselenolates), and poly(1,1-diselenolates) (Se--Se
Bidentates and Se--Se Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Mn.sup.+3 and/or
Mn.sup.+4 include, but are not limited to:
1,1-dicyano-2,2-ethylenediselenolate;
1,1-dicarboalkoxy-2,2-ethylenediselenolate;
1,1-di(trifluoromethyl)-2,2-e- thylene diselenolate;
1,1-di(pentafluorophenyl)-2,2-ethylene diselenolate;
1-pentamethylene-2,2-ethylene diselenolate; and 1-nitroethylene
diselenolate.
[0708] Se Valence Stabilizer #18: Examples of diselenocarbamates,
bis(diselenocarbamates), and pqly(diselenocarbamates) (including
N-hydroxydiselenocarbamates and N-mercaptodiselenocarbamates)
(Se--Se Bidentates, Se--Se Tridentates, and Se--Se Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: dimethyldiselenocarbama- te;
di(trifluorodimethyl)diselenocarbamate; diethyldiselenocarbamate;
dipropyldiselenocarbamate; diisopropyldiselenocarbamate;
dibutyldiselenocarbamate; ditertbutyldiselenocarbamate;
dicyanamidodiselenocarbamate; azidoselenoformates;
diphenyldiselenocarbamate; di(pentafluorophenyl)diselenocarbamate;
dibenzyldiselenocarbamate; dinaphthyldiselenocarbamate;
dicyclohexyldiselenocarbamate; dinorbornyldiselenocarbamate;
diadamantyldiselenocarbamate; pyrrolidinodiselenocarbamate;
piperidinodiselenocarbamate; morpholinodiselenocarbamate;
thiamorpholinodiselenocarbamate; 3-pyrrolinodiselenocarbamate;
pyrrolodiselenocarbamate; oxazolodiselenocarbamate;
isoxazolodiselenocarbamate; thiazolodiselenocarbamate;
isothiazolodiselenocarbamate; indolodiselenocarbamate;
carbazolodiselenocarbamate; pyrazolinodiselenocarbamate;
imidazolinodiselenocarbamate; pyrazolodiselenocarbamate;
imidazolodiselenocarbamate; indazolodiselenocarbamate; and
triazolodiselenocarbamate.
[0709] Se Valence Stabilizer #19: Examples of triselenophosphoric
acids (phosphorotriselenoic acids), bis(triselenophosphoric acids),
poly(triselenophosphoric acids), and derivatives thereof (Se--Se
Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
triselenophosphoric acid, O-phenyltriselenophosphoric acid,
O-benzyltriselenophosphoric acid, O-cyclohexyltriselenophosphoric
acid, O-norbornyltriselenophosphoric acid,
O,Se-diphenyltriselenophosphoric acid,
O,Se-dibenzyltriselenophosph- oric acid,
O,Se-dicyclohexyltriselenophosphoric acid, and
O,Se-dinorbornyltriselenophosphoric acid.
[0710] Se Valence Stabilizer #20: Examples of diselenophosphoric
acids (phosphorodiselenoic acids), bis(diselenophosphoric acids),
poly(diselenophosphoric acids), and derivatives thereof (Se--Se
Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
diselenophosphoric acid, O-phenyldiselenophosphoric acid,
O-benzyldiselenophosphoric acid, O-cyclohexyldiselenophospboric
acid, O-norbornyldiselenophosphoric acid,
O,)-diphenyldiselenophosphoric acid, O,O-dibenzyldiselenophosphoric
acid, O,O-dicyclohexyldiselenophosphoric acid, and
O,O-dinorbornyldiselenophosp- horic acid.
[0711] Se Valence Stabilizer #21: Examples of tetraselenophosphoric
acids (phosphorotetraselenoic acids), bis(tetraselenophosphoric
acids), poly(tetraselenophosphoric acids), and derivatives thereof
(Se--Se Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
tetraselenophosphoric acid, Se-phenyltetraselenophosphoric acid,
Se-benzyltetraselenophosphoric acid,
Se-cyclohexyltetraselenophosphoric acid,
Se-norbornyltetraselenopho- sphoric acid,
Se,Se-diphenyltetraselenophosphoric acid,
Se,Se-dibenzyltetraselenophosphoric acid,
Se,Se-dicyclohexyltetraselenopb- osphoric acid, and
Se,Se-dinorbornyltetraselenophosphoric acid.
[0712] Se Valence Stabilizer #22: Examples of diselenocarbonates,
triselenocarbonates, bis(diselenocarbonates), and
bis(triselenocarbonates- ), (Se--Se Bidentates and S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: Se,Se-diethyldiselenocarbonate- ; Se
Se-diisopropyldiselenocarbonate; Se,Se-diphenyldiselenocarbonate;
Se,Se-dibenzyldiselenocarbonate;
Se,Se-dicyclohexyldiselenocarbonate;
Se,Se-dinorbornyldiselenocarbonate; diethyltriselenocarbonate;
diisopropyltriselenocarbonate; diphenyltriselenocarbonate;
dibenzyltriselenocarbonate; dicyclohexyltriselenocarbonate; and
dinorbornyltriselenocarbonate.
[0713] Se Valence Stabilizer #23: Examples of selenocyanate ligands
(Se monodentates) that meet the requirements for use as "narrow
band" valence stabilizers for Mn.sup.+3 and/or Mn include, but are
not limited to: selenocyanate (--SeCN).
[0714] Se Valence Stabilizer #24: Examples of selenolates (Se
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: selenophenol; and naphthaleneselenol.
[0715] Miscellaneous Valence Stabilizer #1: Examples of diene,
bicyclicand tricyclic hydrocarbon ligands that meet the
requirements for use as "narrow band" valence stabilizers for
Mn.sup.+3 and/or Mn.sup.+4 include, but are not limited to:
cyclopentadiene; azulene; carotene; norbornane; and adamantane.
[0716] Miscellaneous Valence Stabilizer #2: Examples of cyanide and
related ligands that meet the requirements for use as "narrow band"
valence stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are
not limited to: cyanide (--CN); and fulminate (--CNO).
[0717] Miscellaneous Valence Stabilizer #3: Examples of carbonyl
ligands that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: carbonyl (--CO); and carbon dioxide (CO.sub.2)
ligands.
[0718] Miscellaneous Valence Stabilizer #4: Examples of halogens
that meet the requirements for use as "narrow band" valence
stabilizers for Mn.sup.+3 and/or Mn.sup.+4 include, but are not
limited to: fluorine; chlorine; bromine; and iodine.
[0719] Water-soluble precursors for the organic valence stabilizers
are typically used to ensure that sufficient material is available
for pigment synthesis. However, in the case of organic valence
stabilizers, it is also possible to synthesize the desired MnIII or
MnIV/valence stabilizer compounds from organic solvent systems.
Therefore, solubility in organic solvents (for the precursors) is
also acceptable. Identification of suitable water soluble
precursors can be difficult because many of these organics do not
form a wide range of water-soluble compounds.
[0720] 3e) Mixed Inorganic/Organic Valence Stabilizers
[0721] Mixing organic and inorganic valence stabilizers in a
pigment solution will often result in a pigment with poor corrosion
inhibiting properties because of cross interference. Inorganic and
organic stabilizers interact with MnIII and/or MnIV in different
ways. For example, inorganic valence stabilizers perform their
function by forming a shell of octahedrally or square pyramidally
coordinated anionic species around a captured MnIII or MnIV ion.
The net charge of these inorganic MnIII- or MnIV-stabilizer
compounds is therefore always negative. Organic species stabilize
by the formation of a hard or soft bond between the bonding atom in
the stabilizer (e.g., oxygen, nitrogen, or sulfur) and the MnIII or
MnIV ion. The net charge of these compounds is usually positive. If
these two very different types of stabilization ligands are
combined, then the magnitude of the charge on the stabilized
compound can be significantly reduced. The performance of organic
or inorganic stabilized corrosion inhibitor compounds has been
found to be related to the ability of the compound to form and
sustain a thick electrostatic barrier layer. Additionally, a mixed
stabilizer will have a poorly developed electrostatic field and a
non-optimal packing around the MnIII or MnIV ion, resulting in a
compound with less resistance to aqueous attack. Mixed
organic/inorganic stabilized MnIII or MnIV pigments can perform
more poorly than pigments that have exclusively inorganic or
organic valence stabilizers for this reason.
[0722] 4) Additional Solubility Control Agents
[0723] The use of additional solubility control agents is optional.
For example, the anions or cations present in the pigment synthesis
bath useful for preparation of "sparingly soluble" pigments may be
sufficient to form compounds with the desired solubility and
saturated pH characteristics. However, pigment synthesis may
produce compounds with greater than optimal solubilities, and the
use of additional solubility control agents may be desirable. In
situations where fine tuning of solubility or saturated pH is
desired, cationic species are typical for MnIII- or MnIV-stabilizer
combinations when an inorganic valence stabilizer is used, and
anionic species are typical for MnIII or MnIV/organic valence
stabilizer combinations.
[0724] Additional solubility and saturated pH control can be
achieved through the use of nontoxic inorganic cations, which
include, but are not limited to: H.sup.+, Li.sup.+, Na.sup.+,
K.sup.+, Rb.sup.+, Cs.sup.+, NH.sub.4.sup.+, Mg.sup.+2, Ca.sup.+2,
Sr.sup.+2, Y.sup.+3, La.sup.+3, Ce.sup.+3, Ce.sup.+4, Nd.sup.+3,
Pr.sup.+3, Sc.sup.+3, Sm.sup.+3, Eu.sup.+3, EU.sup.+2, Gd.sup.+3,
Tb.sup.+3, Dy.sup.+3, Ho.sup.+3, Er.sup.+3, Tm.sup.+3, Yb.sup.+3,
Lu.sup.+3, Ti.sup.+4, Zr.sup.+4, Ti.sup.+3, Hf.sup.+4, Nb.sup.+5
Ta.sup.+5, Nb.sup.+4, Ta.sup.+4, Mo.sup.+6, W.sup.+6, Mo.sup.+5,
W.sup.+5, Mo.sup.+4, W.sup.+4, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4,
Fe.sup.+2, Fe.sup.+3, Co.sup.+2, Co.sup.+3, Ru.sup.+2, Ru.sup.+3,
Ru.sup.+4, Rh.sup.+3, Ir.sup.+3, Rh.sup.+2, Ir.sup.+2, PD.sup.+4,
Pt.sup.+4, Pd.sup.+2, Pt.sup.+2, Cu.sup.+2, Cu.sup.+2, Cu.sup.+3,
Ag.sup.+, Ag.sup.+2, Ag.sup.+3, Au.sup.+, Au.sup.2, Au.sup.+3,
Zn.sup.+2, Al.sup.+3, Ga.sup.+3, Ga.sup.+, In.sup.+3, In.sup.+,
Ge.sup.+4, Ge.sup.+2, Sn.sup.+2, Sn.sup.+4, Sb.sup.+3, Sb.sup.+5,
Bi.sup.+3, and Bi.sup.+5. Any water-soluble compound containings
these cations can be used for this purpose. The nitrates,
chlorides, bromides, and perchlorates of these cations offer
inexpensive water-soluble precursors, although many other
water-soluble precursors exist. The use of alkaline ions such as
Mg.sup.+2, Ca.sup.+2, and Sr.sup.+2 for solubility control has been
demonstrated successfully, with acceptable saturated pH values.
[0725] Cationic solubility control may also be achieved through the
use of nontoxic organic cations that include, but are not limited
to: quaternary ammonium compounds (NR.sub.4.sup.+, where R can be
any combination of alkyl, aromatic, or acyclic organic
substituents, such as the methyltriethylammonium ion); organic
compounds containings at least one N.sup.+ site (such as pyridinium
or thiazolium cations); organic compounds containing at least one
phosphonium site (P.sup.+, such as the benzyltriphenylphosphonium
ion); organic compounds containing at least one stibonium site
(Sb.sup.+, such as the tetraphenylstibonium ion); organic compounds
containing at least one oxonium site (O.sup.+, such as pyrylium
cations); organic compounds containing at least one sulfonium site
(S.sup.+, such as the triphenylsulfonium ion); and organic
compounds containing at least one iodonium site (I.sup.+, such as
the diphenyliodonium ion).
[0726] The quaternary ammonium compounds, organic compounds
containing at least one N.sup.+ site, and organic compounds
containing at least one oxonium site are the most important of
these classifications because of the very large number of stable
cations that are available. Water-soluble precursors for these
organic cations are desirable in order to maximize the amount of
material available in the appropriate pigment synthesis solution.
Most of these materials are also soluble in organic solvents and
hydrocarbons. Fluorides, chlorides, and bromides offer the most
water-soluble precursors for these organic cations, although
nitrates and perchlorates of those cations with lower molecular
weights (e.g., tetramethylammonium) are also acceptable
water-soluble precursors. Nitrates and perchlorates of larger
(greater molecular weight) organic cations are generally not
acceptable as precursors because of their low water solubility.
[0727] Toxic inorganic or organic cations can be used as additional
solubility control agents although this is less desirable. Examples
of toxic inorganic cations that can be used include, but are not
limited to: Be.sup.+2, Ba.sup.+2, V.sup.+5, V.sup.+4, V.sup.+3,
Cr.sup.+3, Ni.sup.+2, Ni.sup.+4, Os.sup.+4, Cd.sup.+2, Hg.sup.+1,
Hg.sup.+2, Tl.sup.+, Tl.sup.+3, As.sup.+3, As.sup.+5, Pb.sup.+2,
and Pb.sup.+4. Examples of toxic organic cations include, but are
not limited to: organic compounds containing at least one arsonium
site (an example being the tetraphenylarsonium ion of As.sup.+) and
organic compounds containing at least one selenonium site (an
example being the triphenylselenonium ion of Se.sup.+). Use of
these materials for additional solubility control may be necessary
in some specific instances where the toxicity of the resulting
pigment is of limited importance to the operator. Water-soluble
precursors for these toxic cations are typical in order to maximize
the amount of available cation for solubility control in
aqueous-based synthesis solutions. The organic cations are
frequently hydrocarbon-soluble. In general, the nitrates,
chlorides, bromides, and perchlorates of these cations offer the
highest water solubility.
[0728] Additional solubility control can also be achieved by using
nontoxic inorganic anions, especially for MnIII or MnIV/organic
valence stabilizer combinations. Soluble precursors for these
inorganic anions are desirable in order to maximize the amount of
material available in the appropriate pigment formation solution.
Inorganic examples include, but are not limited to:
fluorotitanates, chlorotitanates, fluorozirconates,
chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates,
chlorotantalates, molybdates, tungstates, permanganates,
fluoromanganates, chloromanganates, fluoroferrates, chloroferrates,
fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates,
borates, fluoroborates, fluoroaluminates, chloroaluminates,
carbonates, silicates, fluorosilicates, fluorostannates, nitrates,
nitrites, azides, phosphates, phosphites, phosphonates,
phosphinites, thiophosphates, thiophosphites, thiophosphonates,
thiophosphinites, fluorophosphates, fluoroantimonates,
chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates,
dithionites, dithionates, fluorosulfates, tellurates, fluorides,
chlorides, chlorates, perchlorates, bromides, bromates, iodides,
iodates, periodates, and heteropolyanions (e.g.,
heteropolymolybdates or silicomolybdates).
[0729] Additional solubility control can also be achieved through
the use of an almost unlimited number of nontoxic organic anions
(e.g., organics with different carboxylate or acid groups).
Examples include, but are not limited to: ferricyanides;
ferrocyanides; cyanocobaltates; cyanocuprates; cyanomanganates;
cyanates; cyanatoferrates; cyanatocobaltates; cyanatocuprates;
cyanatomanganates; thiocyanates; thiocyanatoferrates;
thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates;
cyanamides; cyanamidoferrates; cyanamidocobaltates;
cyanamidocuprates; cyanamidomanganates; nitritoferrates;
nitritocobaltates; azides; (thio)carboxylates,
di(thio)carboxylates, tri(thio)carboxylates, or
tetra(thio)carboxylates [useful representatives including, but not
limited to, acetic acid, benzoic acid, succinic acid, fumaric acid,
salicylic acid, lactic acid, tartaric acid, antimonyl tartrates,
cinnamic acid, adipic acid, phthalic acid, terephthalic acid,
citric acid, ascorbic acid, malic acid, malonic acid, oxalic acid,
stearic acid, gallic acid, naphthenic acid, camphoric acid,
nitrosalicylic acid, aminosalicylic acid, acetylsalicylic acid,
sulfosalicylic acid, nitrobenzoic acid, perfluoroC.sub.2-16
carboxylic acids, trinitrobenzoic acid, chlorobenzoic acid, anisic
acid, iodobenzoic acid, anthranilic acid, mandelic acid, toluic
acid, nicotinic acid, isonicotinic acid, pyrazolecarboxylic acid,
picrolonic acid, quinaldic acid, diphenic acid, benzoquinaldic
acid, quinolinecarboxylic acid, isoquinolinecarboxylic acid,
triazinecarboxylic acid, (thio)carbonic acids, (thio)carbamic
acids, trimethylhexylic acid, tetrafluorophthalic acid,
ethylenediaminetetraacetic acid, toluoylpropionic acid, lactobionic
acid, octylthiopropionate, lipoic acid, methylbenzoylpropionic
acid, anthracenesuccinic acid, benzothiazolecarboxylic acid,
phenylacetic acid, glycolic acid, thioglycolic acid,
benzothiazolylthiosuccinic acid, benzothiazolylthiopropionic acid,
phenylanthranilic acid, furancarboxylic acid, nitrofuroic acid,
phosphonobutanetricarboxylic acid benzothiazolylthiosuccinic acid,
N-phosphonomethylglycine, cresoxyacetic acid, aminobutyric acid,
alanine, asparagine, cysteine, glutamine, glycine, leucine,
methionine, phenylalanine, proline, serine, threonine, tryptophan,
tyrosine, valine, glutamic acid, aspartic acid, arginine,
histidine, lysine, trihydroxyglutaric acid, phenoxyacetic acid,
hydroxynaphthoic acid, phenylbutyric acid, hydroxyphosphonoacetic
acid, tropic acid, aminophenylpropionic acid, dihydrocinnamic acid,
hydroxycinnamic acid, cinchomeronic acid, aurintricarboxylic acid,
benzotriazolecarboxylic acid, hydroxyphosphonoacetic acid, cyanuric
acid, barbituric acid, violuric acid, diphenylvioluric acid,
dilituric acid, thiobarbituric acid, cresotic acid,
trimethylhexylic acid, nitrilotriacetic acid,
N,N'-terephthaloylbis(aminocaproic acid),
ethyleneglycolbis(aminoethylether)tetraacetic acid,
diethylenetriaminepentaacetic acid, 2-phosphonobutanetricarboxylic
acid, N,N'-bis(2-hydroxysuccinyl)ethylenediamine, nicotinic acid,
naptalam, nitrobenzoic acid, nonylphenoxyacetic acid, and
olsalazine]; (thio)phenolates, di(thio)phenolates,
tri(thio)phenolates, or tetra(thio)phenolates [useful
representatives including, but not limited to, pyrocatechol,
resorcinol, picric acid, styphnic acid, pyrogallol, purpurin,
purpurogallin, benzopurpurin, gallein, thiophenol, rhodizonic acid,
kojic acid, chromotropic acid, carminic acid, fluorescein, tannic
acid, and humic acid]; (thio)phosphonates, di(thio)phosphonates, or
tri(thio)phosphonates [useful representatives including, but not
limited to, diethylphosphonic acid, diphenylphosphonic acid,
nitrophenylphosphonic acid, perfluoroC.sub.2-16 phosphonic acids,
benzenephosphonic acid, phytic acid, hydroxyethylidenebisphosphonic
acid, nitrilotrimethylenephospbonic acid, aminomethylenephosphonic
acid, etidronic acid, ethylphosphonic acid, chloroethylphosphonic
acid, ethylenediaminotetramethylenephosphonic acid,
laurylhydroxydiphosphonic acid, methylaminodimethylenephosphonic
acid, alkyl(aryl)diphosphonic acids,
N-cetylaininoethanediphosphonic acid, carboxyhydroxymethylphosphon-
ic acid (hpa), oxyethylidenediphosphonic acid,
polycaproamidophosphonates, phenylethanetriphosphonic acid,
oxidronic acid, and pamidronic acid]; (thio)phosphonamides,
di(thio)phosphonamides, or tri(thio)phosphonamides [useful
representatives including, but not limited to, phosphoramidic acid,
phosphordiamidic acid (diamidophosphonic acid), and
phosphoramidothioic acid]; amino(thio)phosphonates,
diamino(thio)phosphonates, or triamino(thio)phosphonates;
imino(thio)phosphonates or diimino(thio)phosphonates;
(thio)sulfonates, di(thio)sulfonates, or tri(thio)sulfonates
[useful representatives including, but not limited to,
methanesulfonic acid, benzenesulfonic acid, aminobenzenesulfonic
acid (sulfanilic acid), nitrobenzenesulfonic acid, phenylsulfonic
acid, naphthalenesulfonic acid, nitronaphthalenesulfonic acid,
oxinesulfonic acid, alizarinsulfonic acid, benzidinesulfonic acid,
flavianic acid, camphorsulfonic acid, diiodophenolsulfonic acid
(sozoiodol), 8-hydroxyquinoline-5-sulfonic acid,
7-nitro-8-hydroxyquinoline-5-sulfonic acid; benzotriazolesulfonic
acid, bis(trifluoromethyl)benzenesulfonic acid,
diiododihydroxybenzopheno- nesulfonic acid,
p-amino-p'-ethoxydiphenylamine-o-sulfonic acid,
1-amino-2-naphthol-4-sulfonic acid;
1,2-diaminoanthraquinone-3-sulfonic acid,
1,5-dinitro-2-naphthol-7-sulfonic acid, perfluoroC.sub.2-16
sulfonic acids, benzenedisulfonic acid, phenyldisulfonic acid,
naphthalenedisulfonic acid, 3,6-naphtholdisulfonic acid,
indigodisulfonic acid, benzidinedisulfonic acid,
carboxyiodobenzenesulfonic acids; N-benzeneaminomethanesulfonic
acid (ams); amido-G-acid; amido-R-acid; naphthalene(di)sulfonic
acid (Armstrong's acid); amsonic acid; Badische acid;
camphorsulfonic acid; chrysophenine; Cassella's acid; chromotropic
acid; Cleve's acid; croceic acid; anthracenesulfonic acid;
hydroxyquinolinesulfonic acid; hydrazinobenzenesulfonic acid;
indigo cannine; indoxyl; isatinsulfonic acid; indican;
lignosulfonic acid; metanil yellow; metanilic acid;
naphthoquinonesulfonic acid; Nuclear Fast Red; naphthol(di)sulfonic
acid; naphthylamine(di)sulfonic acid; Orange I; orthanilic acid;
phenol(di)sulfonic acid; methylenedinapbthalenesulfonic acid;
methyl orange; and piperazinediethanesulfonic acid (pipes)];
(thio)sulfonamides, di(thio)sulfonamides, or tri(thio)sulfonamides;
amino(thio)sulfonates, diamino(thio)sulfonates, or
triamino(thio)sulfonates; imino(thio)sulfonates (including
sulfamates) or diimino(thio)sulfonates (including disulfamates)
[useful representatives including, but not limited to,
methylsulfamic acid and phenylsulfamic acid]; (thio)borates,
di(thio)borates, or (thio)boronates [useful representatives
including, but not limited to, phenylboric acid and borotartaric
acid]; organic silicates; and stibonates [useful representatives
including, but not limited to, antimonyl tartrate and
benzenestibonic acid]. Soluble precursors for these organic anions
are desirable to maximize the amount available in the appropriate
pigment synthesis solution. These organic anions are frequently
soluble in organic solvents or hydrocarbons in addition to
water-based systems.
[0730] Finally, toxic inorganic or organic anions can be used as
additional solubility control agents, although they are less
desirable. Examples of toxic inorganic anions include, but are not
limited to: arsenates, arsenites, fluoroarsenates, chloroarsenates,
selenates, selenites, fluorothallates, chlorothallates, iodomercury
anions (e.g., Nessler's reagent), thiocyanatomercury anions (e.g.,
Behren's reagent), chloromercurates, bromomercurates, osmates,
fluoronickelates, chromates, Reinecke's salt, and vanadates.
Examples of toxic organic anions include cyanides; cyanochromates;
cyanonickelates; cyanatochromates; cyanatonickelates;
thiocyanatochromates; thiocyanatonickelates; cyanamidochromates;
cyanamidonickelates; nitritonickelates; arsonates, diarsonates, or
triarsonates [useful representatives being propylarsonic acid,
phenylarsonic acid, hydroxyphenylarsonic acid, benzenearsonic acid,
methylbenzenearsonic acid, hydroxybenzenearsonic acid, and
nitrobenzenearsonic acid]; and organic selenates, diselenates, or
triselenates. These materials may be necessary in some specific
instances for additional solubility control where toxicity of the
final pigment material is of limited importance. Soluble precursors
for these organic anions are desirable to maximize the amount
available in the appropriate pigment synthesis solution. The alkali
or ammonium species of these anions typically offer the greatest
water solubility.
[0731] Solubility control agents can also be used for "low
solubility" and "insoluble" MnII and MnIV pigments for use as lead
chromate and/or red lead replacements. However, the choice of
solubility control agents is limited due to the chemistry and
preparation methods for these pigments. These pigments are
typically prepared by calcining, firing, or otherwise heating
powder mixtures, so organic solubility control agents are not
acceptable because of thermal degradation. In addition, because
these calcined or fired manganese-containing mixtures result in
complex oxide compounds, there is no need to add anionic solubility
control agents. The only solubility control agents suitable for use
with the "low solubility" or "insoluble" MnII or MnIV pigments will
overwhelmingly be inorganic cations.
[0732] Solubility control agents for calcined, fired, or otherwise
heated MnIII and/or MnIV-containing pigments include, but are not
limited to: Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+,
Be.sup.+2, Mg.sup.+2, Ca.sup.+2, Sr.sup.+2, Ba.sup.+2, Y.sup.+3,
La.sup.+3, Ce.sup.+3, Ce.sup.+.sup.4, Ti.sup.+4, Zr.sup.+4,
V.sup.+5, Nb.sup.+5, Ta.sup.+5, Mo.sup.+6, W.sup.+6, Cr.sup.+3,
Mn.sup.+2, Fe.sup.+3, Fe.sup.+2, Co.sup.+2, Co.sup.+3, Ni.sup.+2,
Cu.sup.+2, Ag.sup.+, Ag.sup.+2, Zn.sup.+2, Al.sup.+3, In.sup.+3,
Sn.sup.+4, Sb.sup.+3, Sb.sup.+5, Bi.sup.+3, and Bi.sup.+5. Table 6
shows example compositions of low solubility or insoluble MnIII or
MnIV compounds suitable as pigments that can be produced for many
of these solubility control cations. It is interesting to note the
similarity between these compositions and those shown in Table I
for naturally-occurring MnIII or MnIV minerals, further validating
their longterm stability. As the solubility control cation is
changed, dramatic differences in solubility can be observed. For
example, Mg-containing MnIII or MnIV pigments (i.e.,
MgM.sub.n.sub.2O.sub.4) exhibit higher solubilities (i.e.,
10.sup.-4 moles/liter MnIII or MnIV) whereas Ba-containing MnIII or
MnIV pigments (i.e., BaMnO.sub.3) exhibit much lower (i.e.,
10.sup.-8 or 10.sup.-9 moles/liter MnIII or MnIV) solubilities. In
this way, even the performance of calcined or fired MnIII or MnIV
ceramic powders can be tailored for specific applications.
Combinations of these ions can also be used to modify
performance.
[0733] It has been noted that one of the primary functionalities of
lead chromate and especially red lead pigments is the ability to
insolubilize corrosive anions (especially sulfate) via the divalent
lead ion. Similar functionality can be achieved using proper choice
of the solubility control agents described above. For example,
barium (Ba.sup.+2) is notorious for its ability to insolubilize
sulfate ions. Bismuth (Bi.sup.+3) can produce insoluble chlorides
under the proper conditions. Therefore, of the cationic solubility
control agents listed above for "low solubility" or "insoluble"
MnIII and MnIV pigments, those containing Ba.sup.+2, Bi.sup.+3, and
Bi.sup.+5 are typical.
[0734] Similarly, compositions containing cations that are
themselves corrosive towards structural metals are less desirable.
Hence, compositions containing potassium (K.sup.+) and especially
sodium (Na.sup.+) are less desirable.
7TABLE 6 Representative Examples of Low Solubility or Insoluble
MnIII or MnIV Pigments Suitable For Lead Chromate or Red Lead
Replacements Solubility Control Cation Example Composition(s)
Comments None MnO.sub.2, Mn.sub.3O.sub.4, Mn.sub.2O.sub.3, No
compositional modification of MnO(OH), Mn(O,OH).sub.2 properties
Lithium (Li.sup.+) LiMn.sub.2O.sub.4 Magnesium (Mg.sup.+2)
MgMn.sub.2O.sub.4 Highest solubility of MgMnO.sub.3 calcined
pigments MgMnO.sub.3 is unstable Solid solutions with
MgAl.sub.2O.sub.4 or MgFe.sub.2O.sub.4 also possible Calcium
(Ca.sup.+2) CaMnO.sub.3, CaMn.sub.2O.sub.4, CaMnO.sub.3 most stable
Ca.sub.2MnO.sub.4 Solid solutions with Co, Fe, Ni, Bi, Ba, Zn, Sr,
La, Ce, and Y formulas also possible Strontium (Sr.sup.+2)
SrMnO.sub.3 Solid solutions with Ca, Zn, Ba, Bi, La, Ce, and Y
formulas also possible Barium (Ba.sup.+2) BaMnO.sub.3,
BaMn.sub.8O.sub.16 Solid solutions with Sr, Ca, Zn, Bi, La, Y, and
Ce formulas also possible Zinc (Zn.sup.+2) ZnMn.sub.2O.sub.4,
ZnMn.sub.3O.sub.7 Solid solutions with Co, Cu, Ni, Fe, Ca, Sr, Ba,
La, Ce, Y, and Bi formulas also possible Bismuth (Bi.sup.+3)
BiMnO.sub.3, BiMn.sub.2O.sub.5 Solid solutions with Ca, Sr, Ba, Zn,
La, Ce, and Y formulas also possible Lanthanum (La.sup.+3)
LaMnO.sub.3 Solid solutions with Sr, Ca, Zn, Ba, Ce, Bi, and Y
formulas also possible Cerium (Ce.sup.+3) CeMnO.sub.3 Solid
solutions with Sr, Ca, Zn, Ba, Bi, La, and Y formulas also possible
Yttrium (Y.sup.+3) YMnO.sub.3 Solid solutions with Sr, Ca, Zn, Ba,
Bi, La, and Ce formulas also possible Aluminum (Al.sup.+3)
AlMn.sub.2O.sub.4 Exhibits higher solubility Somewhat unstable
Cobalt (Co.sup.+2) CoMn.sub.2O.sub.4, CoMn.sub.3O.sub.7 Solid
solutions with Ni, Fe, Zn, Cu, and Ca formulas also possible Nickel
(Ni.sup.+2) NiMn.sub.2O.sub.4, NiMn.sub.3O.sub.7 Solid solutions
with Co, Fe, Zn, Cu, and Ca formulas also possible Iron (Fe.sup.+2)
FeMn.sub.2O.sub.4, FeMn.sub.3O.sub.7 Solid solutions with Co, Ni,
Zn, Cu, and Ca formulas also possible Copper (Cu.sup.+2)
CuMn.sub.2O.sub.5, CuMn.sub.3O.sub.7 Solid solutions with Zn, Co,
Fe, Ni formulas also possible
[0735] 5) Valence Stabilizers for "Indicator Pigments"
[0736] Some heteropolymetallate valence stabilizers for trivalent
or tetravalent manganese pigments have been observed to result in
pigments that change color as the MnIII- or MnIV-stabilizer
compound was exhausted during corrosion. For example,
molybdate-stabilized MnIV pigments are typically moroon in color
after being prepared and combined with a suitable binder system.
These pigments were observed to gradually change from maroon to
royal blue after extended exposure to ASTM B-117 and ASTM G-85
accelerated corrosion testing environments. The rate of color
change was gradual with time and scaled with initiation and
continued corrosion of the substrate. The color change from maroon
to blue is well-documented in the inorganic chemistry literature
for heteropolymolybdates. Numerous studies have shown that the
color change associated with molybdenum blues is due to reduction
of the molybdenum (VI) ion (the valence stabilizer for MnIV in this
example), to the more reduced molybdenum (IV) ion. Other
manganese-containing compounds can exhibit differences in color
with the change in valence of the manganese ion in the pigment
compound. Organometallic literature has many examples of manganese
compounds where an organic trivalent or tetravalent manganese
compound is one color and the divalent compound is a different
color.
[0737] Color changes in the paint can be used as a metric to
determine when the corrosion-inhibiting ability of the pigment has
begun to fail. Alternatively, changes in pigment color hue may
suggest remaining corrosion-inhibiting service life. The color
change behavior is not observed for all MnIII- or MnIV-valence
stabilizer combinations. Those compositions that do exhibit a
significant color change between fully oxidized and reduced valence
states are typical for applications where an indication of the
amount of remaining unreacted pigment is desired. This represents
an advantage over conventional chromate or plumbate pigments which
do not demonstrate a significant color change during reduction.
[0738] B) Pigment Synthesis
[0739] The manganese compounds of the present invention can be
synthesized by many different formation routes, and the synthesis
of specific trivalent or tetravalent manganese compounds is often
found in the general manganese coordination chemistry literature.
The syntheses of several trivalent or tetravalent manganese
compounds suitable for use as pigments are outlined in the Examples
section of this specification.
[0740] The pigments can be synthesized via precipitation routes
(including onto inorganic or organic substrates), by firing of
constituents, by evaporative routes, etc. In general, "sparingly
soluble" MnIII and MnIV pigments are best prepared by precipitation
or evaporation routes, whereas "low solubility" or "insoluble"
MnIII and MnIV pigments are best prepared by firing of
constitutents. Precipitation is a typical synthesis route, for
"sparingly soluble" pigments because: a) it is easiest to control,
b) it allows inorganic valence stabilizers to polymerize, and c)
many organic valence stabilizer precursors are degraded by high
temperatures. Precipitation from aqueous (water-based) solutions is
typical, because the formed trivalent or tetravalent manganese
pigment materials are required to be sparingly soluble in water in
order to function adequately as corrosion-inhibitors. For the more
soluble pigments (i.e., with solubilities as high as
1.times.10.sup.0 moles/liter of trivalent or tetravalent manganese,
for specialized applications), precipitation can be aided by
traditional salting-out methodologies, such as adding salt or
alcohols to further facilitate precipitation. If desired,
precipitation onto or in combination with inert materials such as
oxides, hydroxides, silicates, borates, aluminates, phosphates,
carbonates, titanates, molybdates, tungstates, oxalates, polymers,
etc., can be initiated. An almost infinite variety of colors, hues,
tints, solubilities, saturated pHs, decomposition temperatures,
melting points, and corrosion-inhibiting action can be produced in
pigments based solely on the MnIII or MnIV ions.
[0741] Organic solvents can also be used for the synthesis of these
pigments, especially for many of the organic valence-stabilized
manganese compounds. Conventional organic solvents include, but are
not limited to: methanol, ethanol, n-propanol, isopropanol,
n-butanol, isobutanol, sec-butanol, benzyl alcohol, glycerol,
ethylene glycol, propylene glycol, cresol, cycldhexanol, butyl
carbitol, cellosolve, methyl cellosolve, ethyl lactate, acetone,
methyl ethyl ketone (MEK), diethyl ketone, methyl isobutyl ketone
(MIBK), cyclohexanone, acetophenone, diethyl ether, isopropyl
ether, furan, tetrahydrofuran (THF), dioxane, tetrahydropyran,
methyl formate, ethyl formate, methyl acetate, ethyl acetate,
methyl propionate, ethyl propionate, methyl butyrate, ethyl
butyrate, propylene oxide, acetic acid, propionic acid,
butyrolactone, ethylene carbonate, propylene carbonate,
benzaldehyde, propyl amine, diethyl amine, ethanolamine, aniline,
pyridine, acetonitrile, dimethylformamide (DMF), propionitrile,
nitrobenzene, hexane, cyclohexane, benzene, toluene, xylene, carbon
tetrachloride, chloroform, methylene chloride, dichloroethane,
trichloroethane, trichloroethylene, chlorobenzene, Freon 1113,
carbon disulfide, dimethyl sulfoxide (DMSO), and
hexamethylphosphoric triamide (HMPT). These solvents can be used in
instances where the specific MnIII or MnIV/valence stabilizer is
insoluble in that specific solvent and sparingly soluble in water,
or in instances where evaporative formation of fine particle sizes
is desired.
[0742] A typical MnIV compound with-inorganic valence stabilization
was prepared as follows:
[0743] 1) the stabilizer was dissolved in a minimum of water with
added acetic acid or sodium acetate to buffer the solution to the
proper pH;
[0744] 2) manganese nitrate was dissolved in a separate buffered
water solution;
[0745] 3) the stabilizer solution was heated to near boiling and
the manganese solution added all at once;
[0746] 4) this stabilizer-manganese solution was heated for 15 to
60 minutes with a potassium acetate buffer to initiate inorganic
polymerization of the valence stabilizer in the presence of a
persulfate oxidizer to form tetravalent manganese;
[0747] 5) this solution (mother liquor) was cooled and any
precipitate filtered;
[0748] 6) the mother liquor was separated into five fractions and
an additional solubility control agent was added; and
[0749] 7) each solution from step 6 was ice chilled and
precipitates filtered and dried.
[0750] Solubility control agents Mg, Ca, Zn, Sr, and Ba were used
to obtain a broad spectrum of solubilities with a single
MnIV-valence stabilizer combination. Occasionally a precipitate
would not form with the addition of a "solubility control agent" or
a day of evaporation. This would imply that the target compound was
extremely water soluble and unsuited for use as a pigment.
Conversely, a precipitate would occasionally form immediately on
addition of the last pH buffer or even the oxidizing agent. This
would imply that the target MnIV compound was extremely insoluble
and unsuited for use as a corrosion inhibiting pigment when
incorporating the buffer or oxidizer's cations.
[0751] MnIII and MnIV pigments with organic valence stabilizers
were synthesized in a similar fashion. Water-soluble organic
ligands (i.e., the azo dye examples) allowed the entire synthesis
to be performed in aqueous solution. Valence stabilizers of low
water solubility (i.e., 8-hydroxyquinoline) were complexed in an
isopropanol/water mixture. It was not necessary to carefully
control pH of the organic syntheses because polymerization like
that needed for the heteropolymetallate inorganic stabilizers was
not necessary. Anionic "solubility control agents" such as sulfate,
phosphate, molybdate, tungstate, and phosphomolybdate were used for
the organic examples to form progressively larger compounds with
less solubility.
[0752] The color of MnIII or MnIV pigments depends on the specific
MnIII or MnIV-valence stabilizer combination. Inorganically valence
stabilized MnIII or MnIV compounds ranged from maroon to black. The
color of MnIII and MnIV-pigments incorporating organic valence
stabilizers often matched the color of the valence stabilizer. This
was particularly true of the azo dyes. The colors of the
organically stabilized pigments were orange-yellow ranging to green
or brown.
[0753] Oxidation of divalent manganese to the trivalent or
tetravalent oxidation state can be performed prior to, or after,
compound formation. If trivalent or tetravalent manganese salts are
to be used for synthesis, then additional oxidation may or may not
be necessary, depending upon the synthesis conditions. For example,
a MnIII or MnIV/valence stabilizer coordination compound could be
prepared, or a MnII/valence stabilizer compound could be prepared
and subsequently oxidized to a MnIII or MnIV/valence stabilizer
compound. Oxidation prior to compound formation is typical,
however, to ensure that the stability of the formed compound is
maintained.
[0754] The stability of compounds using the same valence stabilizer
ligand differs significantly because of the difference in size
between the MnII, MnIII, and MnIV ions (67 pm versus 61 pm versus
54 pm). This has to do with the size requirements of the
coordinating ligand. Therefore, one ligand geometry may result in a
very stable MnIII compound, but the same compound containing MnIII
or MnIV can, in many instances, exhibit lower stabilities because
of the difference in size of the ions. Oxidation to the trivalent
or tetravalent state prior to precipitation (or other preparative
methodology) ensures that once recovered, the compound is for the
most part in a usable form.
[0755] Preparation of a divalent manganese compound, with
subsequent oxidation treatment (e.g., via steam, gaseous oxygen,
concentrated liquid oxidizer, etc.) to convert the compound to a
trivalent or tetravalent oxidation state, can degrade the ligand or
the entire compound, or can alter substituent groups on that
ligand. Trivalent or tetravalent manganese/valence stabilizer
complexes having a melting temperature lower than approximately
50.degree. C. can be produced as a low melting solid, or a
liquid-phase inhibitor. They can also be combined with inert
materials in order to provide a solid material. If combination with
inert materials is desired, then the trivalent or tetravalent
corrosion inhibiting compound can be absorbed into, or adsorbed
onto, the surfaces of the inert particles. The particles can be
inorganic (e.g., oxides, hydroxides, phosphates, borates,
silicates, carbonates, aluminates, titanates, molybdates,
tungstates, oxalates, polymers, or combinations thereof) or organic
(e.g., polymeric) in nature.
[0756] If low solubility or insoluble MnIII or MnIV compounds are
desired, then calcining, heating, or firing of mixtures of
compounds in an oxidizing environment represents the simplest route
to formation. Firing temperatures of between about 200 and about
1200.degree. C. typically can be used depending upon the specific
composition. MnII, MnIII, MnIV, or even MnVII precursors can be
used for this preparation.
[0757] Once synthesized, the pigments can then be incorporated into
a wide range of binder systems to afford corrosion protection.
Examples of organic binder systems that can incorporate MnIII or
MnIV corrosion-inhibiting pigments include, but are not limited to:
alkyd-type primers, acrylic primers, polyester primers, epoxy
primers, conductive primers, organic sol-gels, ketimine coatings,
polyvinyl coatings, acrylic thermoplastics, asphaltic and coal tar
thermoplastics, polyamide thermoplastics, polyethylene dispersion
thermoplastics, fluorocarbon thermoplastics, chlorocarbon
thermoplastics, silicone thermosets, polyurethane thermosets,
polyester thermosets, epoxy-amine thermosets, epoxy-amide
thermosets, epoxy-ester thermosets, epoxy-coal tar thermosets,
furane thermosets, phenolic thermosets, butadiene styrene
elastomers, chlorinated rubber elastomers, polysulfonated
elastomers, neoprene elastomers, sulfur-containing rubbers, or
combinations thereof. Examples of inorganic binder systems that can
incorporate MnIII or MnIV pigments include, but are not limited to:
low temperature enamels, low temperature glass frits, carbonaceous
coatings, zeolites, inorganic sol-gels, or combinations
thereof.
EXAMPLES
[0758] In order that the invention may be more readily understood,
reference is made to the following examples, which are intended to
illustrate the invention, but not limit the scope thereof
[0759] 1) Wash Primer Preparation
[0760] The corrosion inhibiting performance of MnIII and MnIV
pigments was evaluated by incorporating them into primer paint
formulations. The acid wash primer paint formulation called out in
DoD-P-15328 [Primer (Wash), Pretreatment (Formulation No. 117 for
Metals)] was used to test the synthesized pigments. The wash primer
is composed of a resin, an acid, a corrosion inhibiting pigment,
powdered talc, and carbon lampblack. The acid content of this wash
primer provides a rigorous initial test of the stability and
performance of the pigments. Other, more benign, polymer-based
binder and resin systems might not separate the compounds based on
their performance as effectively or as rapidly.
[0761] The base solution for the wash primer in this specification
was prepared by mixing 88.3 grams of isopropanol, 31.3 grams of
n-butanol, and 3.8 grams of deionized water with 14 grams of
poly(vinyl butyral) resin (PVB) (Monsanto Butvar B-90.TM.). PVB was
used exclusively throughout testing to avoid preparation and
compositional complications during analysis of pigment performance.
However, the invention is not limited to the use of PVB.
[0762] Acid diluent was prepared by mixing 70 grams of 85%
phosphoric acid, 63 grams of deionized water, and 247 grams of
isopropanol. Finely-ground pigment powder was measured out and
added to 13.74 grams of the base solution for each paint to be
tested. A small amount (0.2 g) of powdered talc (magnesium
silicate) "filler" was added. Lampblack was not added to these
samples. These components were mixed thoroughly by hand and 3.8 g
of phosphoric acid diluent added with further mixing. This rough
processing allowed direct comparisons of pigment performance to be
made without complications due to powder treatments, modifications,
and additives.
[0763] For each pigment to be tested, the primer paint was applied
onto 10 metal substrates -5 precleaned 7075-T6 and 5 precleaned
2024-T3 aluminum substrates. This is not the conventional paint
application procedure for aluminum alloys. Under normal service
conditions, aluminum alloys are first subjected to a hexavalent
chromium-containing conversion coating prior to primer application.
However, the conversion coating was omitted so that the performance
of the pigment alone could be evaluated and not the synergistic
effects of hexavalent chromium (in the conversion coating) or even
of barrier films (in the phosphate or anodized coatings).
[0764] Multiple samples of specific pigment compositions were
prepared and tested. Samples treated with zinc and strontium
chromate were used as comparison standards. The chromate pigments
were prepared identically to those used to test MnIII and MnIV
composition variations.
[0765] 2) Corrosion Testing
[0766] PVB wash primers containing various pigment formulations
were evaluated by exposing them to static salt fog (ASTM B-117) and
cyclic Prohesion.TM. (ASTM G-85.5) accelerated corrosion tests.
ASTM B-117 is a traditional corrosion "proof" test that has little
relation to a real working environment. This accelerated corrosion
test exposes samples to a constant salt-water fog and is a de facto
test of solubility for corrosion inhibitors. B-117 does not
necessarily test the ability of a corrosion inhibitor to actually
inhibit corrosion. This is particularly true of inhibitors and
compounds that have not been fully optimized with respect to
solubility. ASTM G-85.5 (Prohesion.TM.) is a cyclic corrosion test
that more closely resembles real working environments. This
accelerated corrosion test exposes samples to a cycle of fog of
dilute salt and ammonium sulfate at room temperature followed by
forced-air drying at an elevated temperature. This is a more
realistic test of the ability of a compound to inhibit corrosion.
Results of these tests can be combined to gain insight into how a
particular coating or compound will perform relative to a standard
as well as helping identify strengths and weaknesses in the
performance of the material.
[0767] 3) Rating Method
[0768] ASTM D-1654 evaluation standard for painted or coated
specimens subjected to corrosive environments was used to evaluate
the performance of the coatings. After the paint dried for 24
hours, each plate was scribed with an X and the plate edges were
sealed with PVC tape to eliminate corrosion edge effects.
[0769] Two visual observations are associated with this rating
test. Procedure A involves a rating of the failure at the
scribe--the representative creepage of corrosion away from the
scribe. Procedure B involves a rating of the failure in the
unscribed areas in terms of the percentage which shows corrosion
coming through the film. In this way, not only the bulk
corrosion-inhibiting action of a pigment through the binder can be
rated, but also its "throwing power".
[0770] 4) Comparison Examples
[0771] Zinc and strontium chromates are commercial CrVI-based
pigments used extensively to provide corrosion protection to metal
surfaces. These pigments were used as performance baselines to
determine the effectiveness of permanganate-based pigment
compositions developed using the methodology described in this
specification.
[0772] Chromate pigments were precipitated from aqueous solutions
and incorporated into PVB wash primer formulations so that each
primer sample had the same molar quantity of hexavalent chromium.
These primers were then applied to 2024-T3 and 7075-T6 aluminum
alloy samples. After the-samples had dried for 24 hours, they were
scribed and the-edges of each sample taped to eliminate edge
effects. These samples were then exposed to 168 hours of both ASTM
B-117 and G-85.5. Magnesium chromate is so soluble in aqueous
solution that the resin began to cross-link immediately, even
before the phosphoric acid diluent was added to the PVB pigment
mixture. PVB based paints containing magnesium chromate pigments
performed well initially (the first 4 days of the test) but began
to degrade rapidly as the chromate was depleted. Insoluble bismuth
chromate appeared to enhance the effects of corrosion and performed
worse than PVB samples that contained no pigment. Zinc and
strontium species with intermediate aqueous solubility provided the
greatest corrosion inhibition of the chromate pigments when used in
the PVB wash primer.
[0773] Table 7 presents the accelerated corrosion testing results
for bare 2024-T3 and 7075-T6 aluminum alloy test panels treated
with PVB combined with zinc and strontium chromate corrosion
inhibiting pigments. For each pigment, the first row shows the
results on 2024-T3, and the second row shows the results on
7075-T6. The zinc and strontium chromate treated samples performed
well during their period of exposure as is expected from the
current state-of-the-art. Minor differences in performance as a
function of substrate composition were noted.
8TABLE 7 Zinc and Strontium Chromate Pigment Accelerated Corrosion
Test Results 2024-T3 7075-T6 2024-T3 7075-T6 B-117 B-117 G-85 G-85
Hours Stabilizer Proc. A Proc. B Proc. A Proc. B Proc. A Proc. B
Proc. A Proc. B 168 Zn as 1.35 g 10 9 9 9 10 9 9 9 168 zinc
chromate 10 9 9 9 10 9 9 9 168 Sr as 1.51 g 9 9 9 9 9 9 9 9 168
strontium chromate 9 9 9 8 9 9 9 9 168 Evaluated by using ASTM
D-1654 - Painted or Coated Specimens Subjected to Corrosive
Environments.
[0774] 5) MnIII and MnIV Pigments in PVB Resin
[0775] MnIII- and MnIV-valence stabilizer compounds were
synthesized using either published literature procedures, or
standard organometallic synthesis techniques because optimized
MnIII and MnIV corrosion-inhibiting pigment materials are not
commercially available. The pigment syntheses were mainly
aqueous-based precipitation techniques, although some pigments
(i.e., those using some selected organic valence stabilizers)
needed alcohol/water mixtures for the synthesis due to the low
solubility of the valence stabilizer compound in pure water. Table
8 shows the MnIII- and MnIV-valence stabilizer combinations used
for these optimized manganese-containing paints. As can be seen in
Table 8, MnIII and MnIV pigments containing both inorganic and
organic valence stabilizers were formed.
9TABLE 8 Optimized Trivalent and Tetravalent Manganese Pigments
Prepared Synthesis Addendum Pigment Solvent Ions Synthesis Notes
Mn.sup.+3/phosphotungstate H.sub.2O Sr, Ca Other salts (Mg, Ba,
& [11-tungstophospho- Zn) not formed manganate(III)]
Mn.sup.+3/molybdate [9- H.sub.2O Mg, Ca, Zn, Sr, Ba All salts
readily formed. molybdo-manganate(III)] Mn.sup.+3/iodate
[Hexaiodato- H.sub.2O H, Ca, Zn, Sr, Ba H (acid) salt precip. from
manganate(III)] mother liq.; precip. of Ca, Zn, Sr, and Ba salts;
Mg salt not formed Mn.sup.+3/vanadate [3- H.sub.2O Na, Mg, Ca, Zn,
Sr, Na salt precip. from vanado-manganate(III)] Ba mother liq.
Mn.sup.+3/Diethyldithio- H.sub.2O SO.sub.4.sup.-2, PO.sub.4.sup.-3,
WO.sub.4.sup.-2, MoO.sub.4.sup.-2, phoshomolybdate
Mn.sup.+3/2-Mercapto- i-PrOH/H.sub.2O SO.sub.4.sup.-2
SO.sub.4.sup.-2 fm. from mother liq. benzimidazole
Mn.sup.+3/8-Hydroxy- i-PrOH/H.sub.2O SO.sub.4.sup.-2,
PO.sub.4.sup.-3 SO.sub.4.sup.-2 fm. from mother guinoline liq.;
PO.sub.4.sup.-3 on anion addn.
[0776] Table 9 presents the accelerated corrosion testing results
for bare 2024-T3 and 7075-T6 aluminum alloy test panels treated
with inorganically stabilized MnIII and MnIV pigments in PVB, while
Table 10 shows some organically stabilized manganese pigments.
Table 9 shows the samples that were produced, as well as the
pigment contained within them. Note that the molar concentration of
MnIII or MnIV in these paints is much less than that in the zinc
chromate primers (7.44.times.10.sup.-3 M). This was done because
the molecular weight of the MnIII or MnIV compounds exceeds that of
zinc chromate, implying that a much larger mass would be necessary
to achieve equal molar concentrations of MnIII or MnIV and CrVI. As
can be seen in the corrosion exposure results, even with these much
lower molar concentrations of MnIII or MnIV, the "optimized"
pigments provided comparable or substantial corrosion protection
compared to chromium. These pigments also outperformed by a
significant margin those pigments (i.e., molybdates, tungstates,
phosphates, borates, cyanamides) containing no inheremt oxidizer
properties. For each pigment, the first row shows the performance
of one sample under the specified conditions, and the second shows
the performance of a duplicate sample under the same conditions. It
is also interesting to note the change in performance for the
MnIII/MnIV pigments just by altering the solubility control
agents.
10TABLE 9 Inorganically Stabilized MnIII and Mn IV Wash Primers
Formulations Stabilizer Inhibitor B-117 B-117 G-85 G-85 Solubility
Control Agent Conc. (M) Proc. A Proc. B Proc. A Proc. B Hours Ca as
1.42 g calcium 7.44 .times. 10.sup.-4 6 3 5 4 6 5 7 6 117
9-molybdomanganate (10% of Cr) 6 3 5 4 6 5 7 6 117 Zn as 1.48 g
zinc 7.44 .times. 10.sup.-4 5 3 5 4 7 7 7 7 117 9-molybdomanganate
(10% of Cr) 5 3 5 3 7 6 8 7 117 Sr as 1.53 g strontium 7.44 .times.
10.sup.-4 5 -- 4 -- 6 5 6 5 117 9-molybdomanganate (10% of Cr) 5 --
5 -- 6 5 6 5 117 Ba as 1.64 g barium 1.64 .times. 10.sup.-4 4 -- 3
-- 7 6 8 7 117 9-molybdomanganate (10% of Cr) 4 -- 3 -- 7 6 7 6 117
Ba as 2.06 g barium 1.49 .times. 10.sup.-3 5 3 5 3 7 7 8 8 144
hexaiodatomanganate (20% of Cr) 5 3 5 3 8 8 7 7 144 Mg as 1.28 g
7.44 .times. 10.sup.-4 9 7 7 8 7 6 6 5 139 magnesium (10% of Cr)
13-vanadatomanganate 9 7 7 8 7 6 7 6 139 Ca as 1.32 g calcium 7.44
.times. 10.sup.-4 8 7 7 6 7 6 7 6 139 13-vanadatomanganate (10% of
Cr) 8 7 7 6 7 6 7 6 139 Zn as 1.37 g zinc 7.44 .times. 10.sup.-4 8
9 7 8 7 6 7 6 139 13-vanadatomanganate (10% of Cr) 8 9 7 8 7 5 6 5
139 Sr as 1.42 g strontium 7.44 .times. 10.sup.-4 7 6 7 6 6 5 6 5
139 13-vanadatomanganate (10% of Cr) 7 6 7 6 6 6 6 6 139 Ba as 1.53
g barium 7.44 .times. 10.sup.-4 7 8 7 6 6 6 6 5 139
13-vanadatomanganate (10% of Cr) 7 7 7 6 7 6 6 5 139 Evaluated by
using ASTM D-1654 - Painted or Coated Specimens Subjected to
Corrosive Environments.
[0777]
11TABLE 10 Organically Stabilized MnIII and Mn IV Wash Primers
Formulations Stabilizer/ Inhibitor B-117 B-117 G-85 G-85 Solubility
Control Agent Conc. (M) Proc. A Proc. B Proc. A Proc. B Hours
Mn.sup.+4/DEDT/ 1.49 .times. 10.sup.-3 6 5 7 6 168 sulfate (20% of
Cr) 6 5 7 5 168 Mn.sup.+4/DEDT/ 1.49 .times. 10.sup.-3 7 5 8 7 168
phosphate (20% of Cr) 7 5 8 7 168 Mn.sup.+4/DEDT/ 1.49 .times.
10.sup.-3 7 6 7 5 168 molybdate (20% of Cr) 7 6 7 5 168
Mn.sup.+4/DEDT/ 1.49 .times. 10.sup.-3 7 5 7 5 168 tungstate (20%
of Cr) 7 5 7 5 168 Mn.sup.+3/MBI/ 1.49 .times. 10.sup.-3 7 7 6 6
168 sulfate (20% of Cr) 8 7 6 6 168 Mn.sup.+3/HQ/ 1.49 .times.
10.sup.-3 6 5 6 5 168 sulfate (20% of Cr) 6 5 6 5 168 Mn.sup.+3/HQ/
1.49 .times. 10.sup.-3 7 6 8 7 168 phosphate (20% of Cr) 7 6 8 7
168 Evaluated by using ASTM D-1654 - Painted or Coated Specimens
Subjected to Corrosive Environments. DEDT = diethyldithiocarbamate,
MBI = mercaptobenzimidazole, HQ = hydroxyquinoline
[0778] Table 10 shows the results for a few of the organic valence
stabilizers evaluated. Due to low substrate supplies, these
pigments were only tested on duplicate 2024-T3 aluminum alloy under
both ASTM B-117 and G-85 conditions. The molar concentration of
MnIII and MnIV in these pigments were also much less than in the
standard chromate pigments. Clear progressions in the performance
of these pigments as a function of anionic solubility control
agents were also observed.
[0779] 6) Calcined MnIII and MnIV Pigments
[0780] Calcined MnIII and MnIV pigments were prepared by mixing
oxides, hydroxides, or peroxides of Mg, Ca, Sr, Ba, Zn, Bi, Co, Ni,
or Fe with manganese oxides such as Mn.sub.2O.sub.3 or MnO.sub.2
and firing in air for up to four hours between 400 and 715.degree.
C..+-.10.degree. C. The ceramic oxide pigments were mixed 1:1 by
weight with boiled linseed oil. This mixture was painted on to bare
1008 carbon steel sheet that had been prepared with an alkaline
cleaning treatment. An identical steel specimen was painted with
red-lead (Pb3O4) and boiled linseed for use as a comparison
standard. The painted test panels were allowed to dry for 48 hours,
X scribed completely through the coating, and then exposed to ASTM
B 117 for 41 hours.
[0781] The Ca-, Zn-, and Sr-containing pigments demonstrated
corrosion inhibition performance equal to that of the of the red
lead pigments in a side by side comparison. The Ba-containing
pigment performed nearly as well as Ca, Zn, and Sr formulations by
providing a high degree of surface protection but not quite as good
as the red lead standard.
[0782] Chromium- or lead-free pigments based on MnIII and/or MnIV
which can be used as replacements for the current CrVI or PbIV
pigments can be made. Many synthesis methodologies and procedures
are available for those skilled in the art of coordination compound
synthesis to produce a multitude of MnIII and/or MnIV corrosion
inhibiting pigments. One or two synthesis procedures or solvents
are likely to be typical for specific MnIII- or MnIV-valence
stabilizer combinations. The methodology described in this
specification encompasses the entire range of valence stabilized
MnIII or MnIV pigment formulations.
[0783] Pigments formed in accordance with the prior art are not
competitive with the present invention. Prior art embodiments
require the use of application processes and chemical compounds
that do not form pigments containing valence stabilized MnIII- or
MnIV-based active corrosion inhibitors that perform equivalent to
current effective commercial hexavalent chromium- or tetravalent
lead-based pigment systems.
[0784] While the invention has been described by reference to
certain embodiments, it should be understood that numerous changes
could be made within the spirit and scope of the inventive concepts
described. Accordingly, it is intended that the invention not be
limited to the disclosed embodiments, but that it have the full
scope permitted by the language of the following claims.
* * * * *