U.S. patent application number 13/915320 was filed with the patent office on 2014-03-06 for polymers of ethylene oxide and carbon dioxide.
The applicant listed for this patent is Cornell University. Invention is credited to Scott ALLEN, Tsuyoshi ANDO, Geoffrey W. COATES.
Application Number | 20140066591 13/915320 |
Document ID | / |
Family ID | 40785587 |
Filed Date | 2014-03-06 |
United States Patent
Application |
20140066591 |
Kind Code |
A1 |
COATES; Geoffrey W. ; et
al. |
March 6, 2014 |
POLYMERS OF ETHYLENE OXIDE AND CARBON DIOXIDE
Abstract
The present disclosure is directed, in part, to methods of
synthesizing a poly(ethylene carbonate) polymer from the reaction
of ethylene oxide (EO) and carbon dioxide (CO.sub.2) in the
presence of a metal complex. The present disclosure also provides
novel metal complexes. In one aspect, the metal complex is of the
formula (I), wherein R.sup.1, R.sup.2, R.sup.3, M, X and Ring A are
as defined herein. ##STR00001##
Inventors: |
COATES; Geoffrey W.;
(Lansing, NY) ; ALLEN; Scott; (Ithaca, NY)
; ANDO; Tsuyoshi; (Ikoma, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cornell University |
Ithaca |
NY |
US |
|
|
Family ID: |
40785587 |
Appl. No.: |
13/915320 |
Filed: |
June 11, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12990202 |
Dec 17, 2010 |
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PCT/US2009/042926 |
May 6, 2009 |
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13915320 |
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61052061 |
May 9, 2008 |
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Current U.S.
Class: |
528/405 ;
556/34 |
Current CPC
Class: |
C08G 64/34 20130101;
C07F 15/065 20130101; C08G 64/183 20130101; C08G 64/0208
20130101 |
Class at
Publication: |
528/405 ;
556/34 |
International
Class: |
C08G 64/34 20060101
C08G064/34 |
Claims
1-140. (canceled)
141. A metal complex of the formula: ##STR00091## wherein: M is a
metal selected from zinc, cobalt, chromium, aluminum, titanium,
ruthenium or manganese; X is absent or is a nucleophilic ligand;
ring A forms an optionally substituted 5- to 6-membered ring; each
R.sup.3 is, independently, selected from hydrogen, halogen,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, and optionally
substituted heteroaryl; R.sup.7 and R.sup.9 are, independently,
selected from hydrogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl; and characterized in that
R.sup.9 has a molecular volume at least two times greater than the
molecular volume of R.sup.7.
142. The metal complex of claim 141, wherein the molecular volume
of R.sup.9 is at least 3 times larger than the molecular volume of
R.sup.7.
143. The metal complex of claim 141, wherein an A-value of R.sup.9
is at least two times larger than an A-value for R.sup.7.
144. The metal complex of claim 141, wherein the A-value of R.sup.9
is greater than about 2.5 kcal/mol.
145. The metal complex of claim 141, wherein the A-value of R.sup.9
is greater than about 3 kcal/mol.
146. The metal complex of claim 141, wherein the A-value of R.sup.9
is greater than about 4 kcal/mol.
147. The metal complex of claim 141, wherein each R.sup.3 is
hydrogen.
148. The metal complex of claim 141, wherein the complex is of the
formula: ##STR00092##
149. The metal complex of claim 141, wherein M is cobalt or
chromium.
150. The metal complex of claim 141, wherein M is cobalt (III).
151. A method of synthesizing a poly(ethylene carbonate) polymer,
the method comprising reacting ethylene oxide and carbon dioxide in
the presence of a metal complex of the formula: ##STR00093##
wherein: M is a metal selected from zinc, cobalt, chromium,
aluminum, titanium, ruthenium or manganese; X is absent or is a
nucleophilic ligand; ring A forms an optionally substituted 5- to
6-membered ring; each R.sup.3 is, independently, selected from
hydrogen, halogen, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl, and
optionally substituted heteroaryl; R.sup.7 and R.sup.9 are,
independently, selected from hydrogen, optionally substituted
aliphatic, optionally substituted heteroaliphatic, optionally
substituted aryl, optionally substituted heteroaryl; and
characterized in that R.sup.9 has a molecular volume at least two
times greater than the molecular volume of R.sup.7.
152. The method of claim 151, wherein the molecular volume of
R.sup.9 is at least 3 times larger than the molecular volume of
R.sup.7.
153. The method of claim 151, wherein an A-value of R.sup.9 is at
least two times larger than an A-value for R.sup.7.
154. The method of claim 151, wherein the A-value of R.sup.9 is
greater than about 2.5 kcal/mol.
155. The method of claim 151, wherein the A-value of R.sup.9 is
greater than about 3 kcal/mol.
156. The method of claim 151, wherein the A-value of R.sup.9 is
greater than about 4 kcal/mol.
157. The method of claim 151, wherein each R.sup.3 is hydrogen.
158. The method of claim 151, wherein the complex is of the
formula: ##STR00094##
159. The method of claim 151, wherein M is cobalt or chromium.
160. The method of claim 151, wherein M is cobalt (III).
Description
PRIORITY CLAIM
[0001] This application claims priority to U.S. Provisional Patent
Application Ser. No. 61/052,061, filed May 9, 2008. The entire
contents of this priority application are incorporated herein by
reference.
BACKGROUND
[0002] Poly(ethylene carbonate) (PEC) is a flexible, biocompatible,
and biodegradable material with high gas barrier properties,
particularly for O.sub.2. It is made via the ring opening
polymerization of ethylene carbonate (EC) or by the
copolymerization of ethylene oxide (EO) and CO.sub.2. Ring opening
polymerization of EC initiated by KOH or Sn(OAc).sub.2 at high
temperature leads to poly(ethylene oxide-co-ether carbonate) rather
than PEC. The high reaction temperatures required for this route
cause the elimination of CO.sub.2 during polymerization. The
alternating copolymerization of epoxides and CO.sub.2 to form
polycarbonates was originally discovered by Inoue in 1969. Since
then, numerous catalyst systems have been developed for
epoxide/CO.sub.2 copolymerization (see, for example, Coates and
Moore, Angew. Chem. Int. Ed. 2004, 43, 6618-6639; Super and
Beckman, Trends Polym. Sci. 1997, 5, 236-240; Darensbourg, and
Holtcamp, Coord. Chem. Rev. 1996, 153, 155-174). Various systems
for EO/CO.sub.2 copolymerization based on Zn, Al, or double metal
cyanide species have been reported; however, they require high
CO.sub.2 pressure and suffer from low catalytic activities.
SUMMARY
[0003] The present disclosure provides, in part, methods of
synthesizing poly(ethylene carbonate) polymers from the reaction of
ethylene oxide (EO) and carbon dioxide (CO.sub.2) in the presence
of a metal complex. The present disclosure also provides novel
metal complexes. In particular, the inventors have found that
N,N'-bis(salicydene)-1,2-cyclohexyldiamine (salcy) metal complexes
are effective in this polymerization reaction, and particularly in
providing poly(ethylene carbonate) polymers with low ether
content.
[0004] In one aspect, the metal complexes as described herein are
of the formula (I):
##STR00002##
wherein:
[0005] M is a metal selected from zinc, cobalt, chromium, aluminum,
titanium, ruthenium or manganese;
[0006] X is absent or is a nucleophilic ligand;
[0007] each instance of R.sup.1, R.sup.2, and R.sup.3 is,
independently, selected from hydrogen, halogen, optionally
substituted aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, and optionally substituted heteroaryl,
or R.sup.1 and R.sup.2, or R.sup.2 and R.sup.3, are joined to form
an optionally substituted aryl or optionally substituted heteroaryl
ring; and
[0008] Ring A forms an optionally substituted 5- to 6-membered
ring.
[0009] In another aspect, the present disclosure provides a method
of synthesizing a poly(ethylene carbonate) polymer, wherein the
polymer is made up of Y, and optionally Z, and wherein the
percentage of Y is greater than the percentage of Z,
##STR00003##
[0010] the method comprising reacting ethylene oxide and carbon
dioxide in the presence of a metal complex.
[0011] In certain embodiments, the above method comprises a metal
complex of formula (I), as described above and herein.
[0012] This application refers to various issued patent, published
patent applications, journal articles, and other publications, all
of which are incorporated herein by reference.
[0013] The details of one or more embodiments are set forth
herein.
DEFINITIONS
[0014] Definitions of specific functional groups and chemical terms
are described in more detail below. For purposes of this
disclosure, the chemical elements are identified in accordance with
the Periodic Table of the Elements, CAS version, Handbook of
Chemistry and Physics, 75.sup.th Ed., inside cover, and specific
functional groups are generally defined as described therein.
Additionally, general principles of organic chemistry, as well as
specific functional moieties and reactivity, are described in
Organic Chemistry, Thomas Sorrell, University Science Books,
Sausalito, 1999; Smith and March March's Advanced Organic
Chemistry, 5.sup.th Edition, John Wiley & Sons, Inc., New York,
2001; Larock, Comprehensive Organic Transformations, VCH
Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods
of Organic Synthesis, 3.sup.rd Edition, Cambridge University Press,
Cambridge, 1987; the entire contents of each of which are
incorporated herein by reference.
[0015] Certain compounds of the present disclosure can comprise one
or more asymmetric centers, and thus can exist in various isomeric
forms, e.g., stereoisomers and/or diastereomers. Thus, inventive
compounds and compositions thereof may be in the form of an
individual enantiomer, diastereomer or geometric isomer, or may be
in the form of a mixture of stereoisomers. In certain embodiments,
the compounds of the disclosure are enantiopure compounds. In
certain other embodiments, mixtures of stereoisomers or
diastereomers are provided.
[0016] Furthermore, certain compounds, as described herein may have
one or more double bonds that can exist as either the Z or E
isomer, unless otherwise indicated.
[0017] The disclosure additionally encompasses the compounds as
individual isomers substantially free of other isomers and
alternatively, as mixtures of various isomers, e.g., racemic
mixtures of stereoisomers. In addition to the above-mentioned
compounds per se, this disclosure also encompasses pharmaceutically
acceptable derivatives of these compounds and compositions
comprising one or more compounds.
[0018] Where a particular enantiomer is preferred, it may, in some
embodiments be provided substantially free of the opposite
enantiomer, and may also be referred to as "optically enriched."
"Optically-enriched," as used herein, means that the compound is
made up of a significantly greater proportion of one enantiomer. In
certain embodiments the compound is made up of at least about 90%
by weight of a preferred enantiomer. In other embodiments the
compound is made up of at least about 95%, 98%, or 99% by weight of
a preferred enantiomer. Preferred enantiomers may be isolated from
racemic mixtures by any method known to those skilled in the art,
including chiral high pressure liquid chromatography (HPLC) and the
formation and crystallization of chiral salts or prepared by
asymmetric syntheses. See, for example, Jacques, et al.,
Enantiomers, Racemates and Resolutions (Wiley Interscience, New
York, 1981); Wilen, S. H., et al., Tetrahedron 33:2725 (1977);
Eliel, E. L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY,
1962); Wilen, S. H. Tables of Resolving Agents and Optical
Resolutions p. 268 (E. L. Eliel, Ed., Univ. of Notre Dame Press,
Notre Dame, Ind. 1972).
[0019] The terms "halo" and "halogen" as used herein refer to an
atom selected from fluorine (fluoro, --F), chlorine (chloro, --Cl),
bromine (bromo, --Br), and iodine (iodo, --I).
[0020] The term "aliphatic" or "aliphatic group", as used herein,
denotes a hydrocarbon moiety that may be straight-chain (i.e.,
unbranched), branched, or cyclic (including fused, bridging, and
spiro-fused polycyclic) and may be completely saturated or may
contain one or more units of unsaturation, but which is not
aromatic. Unless otherwise specified, aliphatic groups contain 1-12
carbon atoms. In certain embodiments, aliphatic groups contain 1-8
carbon atoms. In certain embodiments, aliphatic groups contain 1-6
carbon atoms. In some embodiments, aliphatic groups contain 1-5
carbon atoms, in some embodiments, aliphatic groups contain 1-4
carbon atoms, in yet other embodiments aliphatic groups contain 1-3
carbon atoms, and in yet other embodiments aliphatic groups contain
1-2 carbon atoms. Suitable aliphatic groups include, but are not
limited to, linear or branched, alkyl, alkenyl, and alkynyl groups,
and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl
or (cycloalkyl)alkenyl.
[0021] The term "unsaturated", as used herein, means that a moiety
has one or more double or triple bonds.
[0022] The terms "cycloaliphatic", "carbocycle", or "carbocyclic",
used alone or as part of a larger moiety, refer to a saturated or
partially unsaturated cyclic aliphatic monocyclic or bicyclic ring
systems, as described herein, having from 3 to 12 members, wherein
the aliphatic ring system is optionally substituted as defined
above and described herein. Cycloaliphatic groups include, without
limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl,
cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl,
cyclooctenyl, and cyclooctadienyl. In some embodiments, the
cycloalkyl has 3-6 carbons. The terms "cycloaliphatic",
"carbocycle" or "carbocyclic" also include aliphatic rings that are
fused to one or more aromatic or nonaromatic rings, such as
decahydronaphthyl or tetrahydronaphthyl, where the radical or point
of attachment is on the aliphatic ring.
[0023] The term "alkyl," as used herein, refers to saturated,
straight- or branched-chain hydrocarbon radicals derived from an
aliphatic moiety containing between one and six carbon atoms by
removal of a single hydrogen atom. Unless otherwise specified,
alkyl groups contain 1-12 carbon atoms. In certain embodiments,
alkyl groups contain 1-8 carbon atoms. In certain embodiments,
alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl
groups contain 1-5 carbon atoms, in some embodiments, alkyl groups
contain 1-4 carbon atoms, in yet other embodiments alkyl groups
contain 1-3 carbon atoms, and in yet other embodiments alkyl groups
contain 1-2 carbon atoms. Examples of alkyl radicals include, but
are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl,
iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl,
neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl,
n-undecyl, dodecyl, and the like.
[0024] The term "alkenyl," as used herein, denotes a monovalent
group derived from a straight- or branched-chain aliphatic moiety
having at least one carbon-carbon double bond by the removal of a
single hydrogen atom. Unless otherwise specified, alkenyl groups
contain 2-12 carbon atoms. In certain embodiments, alkenyl groups
contain 2-8 carbon atoms. In certain embodiments, alkenyl groups
contain 2-6 carbon atoms. In some embodiments, alkenyl groups
contain 2-5 carbon atoms, in some embodiments, alkenyl groups
contain 2-4 carbon atoms, in yet other embodiments alkenyl groups
contain 2-3 carbon atoms, and in yet other embodiments alkenyl
groups contain 2 carbon atoms. Alkenyl groups include, for example,
ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the
like.
[0025] The term "alkynyl," as used herein, refers to a monovalent
group derived from a straight- or branched-chain aliphatic moiety
having at least one carbon-carbon triple bond by the removal of a
single hydrogen atom. Unless otherwise specified, alkynyl groups
contain 2-12 carbon atoms. In certain embodiments, alkynyl groups
contain 2-8 carbon atoms. In certain embodiments, alkynyl groups
contain 2-6 carbon atoms. In some embodiments, alkynyl groups
contain 2-5 carbon atoms, in some embodiments, alkynyl groups
contain 2-4 carbon atoms, in yet other embodiments alkynyl groups
contain 2-3 carbon atoms, and in yet other embodiments alkynyl
groups contain 2 carbon atoms. Representative alkynyl groups
include, but are not limited to, ethynyl, 2-propynyl (propargyl),
1-propynyl, and the like.
[0026] The term "aryl" used alone or as part of a larger moiety as
in "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic
and polycyclic ring systems having a total of five to 20 ring
members, wherein at least one ring in the system is aromatic and
wherein each ring in the system contains three to twelve ring
members. The term "aryl" may be used interchangeably with the term
"aryl ring". In certain embodiments of the present disclosure,
"aryl" refers to an aromatic ring system which includes, but is not
limited to, phenyl, biphenyl, naphthyl, anthracyl and the like,
which may bear one or more substituents. Also included within the
scope of the term "aryl", as it is used herein, is a group in which
an aromatic ring is fused to one or more additional rings, such as
benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl,
or tetrahydronaphthyl, and the like.
[0027] The terms "heteroaryl" and "heteroar-", used alone or as
part of a larger moiety, e.g., "heteroaralkyl", or
"heteroaralkoxy", refer to groups having 5 to 14 ring atoms,
preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 .pi.
electrons shared in a cyclic array; and having, in addition to
carbon atoms, from one to five heteroatoms. The term "heteroatom"
refers to nitrogen, oxygen, or sulfur, and includes any oxidized
form of nitrogen or sulfur, and any quaternized form of a basic
nitrogen. Heteroaryl groups include, without limitation, thienyl,
furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,
oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,
thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,
indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
The terms "heteroaryl" and "heteroar-", as used herein, also
include groups in which a heteroaromatic ring is fused to one or
more aryl, cycloaliphatic, or heterocyclyl rings, where the radical
or point of attachment is on the heteroaromatic ring. Nonlimiting
examples include indolyl, isoindolyl, benzothienyl, benzofuranyl,
dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl,
isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl,
4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl,
phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and
pyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono-
or bicyclic. The term "heteroaryl" may be used interchangeably with
the terms "heteroaryl ring", "heteroaryl group", or
"heteroaromatic", any of which terms include rings that are
optionally substituted. The term "heteroaralkyl" refers to an alkyl
group substituted by a heteroaryl, wherein the alkyl and heteroaryl
portions independently are optionally substituted.
[0028] As used herein, the terms "heterocycle", "heterocyclyl",
"heterocyclic radical", and "heterocyclic ring" are used
interchangeably and refer to a stable 5- to 7-membered monocyclic
or 7-14-membered bicyclic heterocyclic moiety that is either
saturated or partially unsaturated, and having, in addition to
carbon atoms, one or more, preferably one to four, heteroatoms, as
defined above. When used in reference to a ring atom of a
heterocycle, the term "nitrogen" includes a substituted nitrogen.
As an example, in a saturated or partially unsaturated ring having
0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the
nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in
pyrrolidinyl), or .sup.+NR (as in N-substituted pyrrolidinyl).
[0029] A heterocyclic ring can be attached to its pendant group at
any heteroatom or carbon atom that results in a stable structure
and any of the ring atoms can be optionally substituted. Examples
of such saturated or partially unsaturated heterocyclic radicals
include, without limitation, tetrahydrofuranyl, tetrahydrothienyl,
pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl,
tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl,
oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl,
oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms
"heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic
group", "heterocyclic moiety", and "heterocyclic radical", are used
interchangeably herein, and also include groups in which a
heterocyclyl ring is fused to one or more aryl, heteroaryl, or
cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl,
phenanthridinyl, or tetrahydroquinolinyl, where the radical or
point of attachment is on the heterocyclyl ring. A heterocyclyl
group may be mono- or bicyclic. The term "heterocyclylalkyl" refers
to an alkyl group substituted by a heterocyclyl, wherein the alkyl
and heterocyclyl portions independently are optionally
substituted.
[0030] As used herein, the term "partially unsaturated" refers to a
ring moiety that includes at least one double or triple bond. The
term "partially unsaturated" is intended to encompass rings having
multiple sites of unsaturation, but is not intended to include aryl
or heteroaryl moieties, as herein defined.
[0031] As described herein, compounds of the disclosure may contain
"optionally substituted" moieties. In general, the term
"substituted", whether preceded by the term "optionally" or not,
means that one or more hydrogens of the designated moiety are
replaced with a suitable substituent. Unless otherwise indicated,
an "optionally substituted" group may have a suitable substituent
at each substitutable position of the group, and when more than one
position in any given structure may be substituted with more than
one substituent selected from a specified group, the substituent
may be either the same or different at every position. Combinations
of substituents envisioned by this disclosure are preferably those
that result in the formation of stable or chemically feasible
compounds. The term "stable", as used herein, refers to compounds
that are not substantially altered when subjected to conditions to
allow for their production, detection, and, in certain embodiments,
their recovery, purification, and use for one or more of the
purposes disclosed herein.
[0032] Suitable monovalent substituents on a substitutable carbon
atom of an "optionally substituted" group are independently
halogen; --(CH.sub.2).sub.0-4R.sup.o; --(CH.sub.2).sub.0-4OR.sup.o;
--O--(CH.sub.2).sub.0-4C(O)OR.sup.o;
--(CH.sub.2).sub.0-4CH(OR.sup.o).sub.2;
--(CH.sub.2).sub.0-4SR.sup.o; --(CH.sub.2).sub.0-4Ph, which may be
substituted with R.sup.o; --(CH.sub.2).sub.0-4O(CH.sub.2).sub.0-1Ph
which may be substituted with R.sup.o; --CH.dbd.CHPh, which may be
substituted with R.sup.o; --NO.sub.2; --CN; --N.sub.3;
--(CH.sub.2).sub.0-4N(R.sup.o).sub.2;
--(CH.sub.2).sub.0-4N(R.sup.o)C(O)R.sup.o; --N(R.sup.o)C(S)R.sup.o;
--(CH.sub.2).sub.0-4N(R.sup.o)C(O)NR.sup.o.sub.2;
--N(R.sup.o)C(S)NR.sup.o.sub.2;
--(CH.sub.2).sub.0-4N(R.sup.oC(O)OR.sup.o;
--N(R.sup.oN(R.sup.oC(O)R.sup.o;
--N(R.sup.o)N(R.sup.o)C(O)NR.sup.o.sub.2;
--N(R.sup.o)N(R.sup.oC(O)OR.sup.o; --(CH.sub.2).sub.0-4C(O)R.sup.o;
--C(S)R.sup.o; --(CH.sub.2).sub.0-4C(O)OR.sup.o;
--(CH.sub.2).sub.0-4C(O)N(R.sup.o).sub.2;
--(CH.sub.2).sub.0-4C(O)SR.sup.o;
--(CH.sub.2).sub.0-4C(O)OSiR.sup.o.sub.3;
--(CH.sub.2).sub.0-4OC(O)R.sup.o; --OC(O)(CH.sub.2).sub.0-4SR--,
SC(S)SR.sup.o; --(CH.sub.2).sub.0-4SC(O)R.sup.o;
--(CH.sub.2).sub.0-4C(O)NR.sup.o.sub.2; --C(S)NR.sup.o.sub.2;
--C(S)SR.sup.o; --SC(S)SR.sup.o,
--(CH.sub.2).sub.0-4OC(O)NR.sup.o.sub.2; --C(O)N(OR.sup.o)R.sup.o;
--C(O)C(O)R.sup.o; --C(O)CH.sub.2C(O)R.sup.o;
--C(NOR.sup.o)R.sup.o; --(CH.sub.2).sub.0-4S SR.sup.o;
--(CH.sub.2).sub.0-4S(O).sub.2R.sup.o;
--(CH.sub.2).sub.0-4S(O).sub.2OR.sup.o;
--(CH.sub.2).sub.0-4OS(O).sub.2R.sup.o; --S(O).sub.2NR.sup.o.sub.2;
--(CH.sub.2).sub.0-4S(O)R.sup.o;
--N(R.sup.o)S(O).sub.2NR.sup.o.sub.2;
--N(R.sup.o)S(O).sub.2R.sup.o; --N(OR.sup.oR.sup.o;
--C(NH)NR.sup.o.sub.2; --P(O).sub.2R.sup.o; --P(O)RO.sub.2;
--OP(O)RO.sub.2; --OP(O)(OR.sup.o.sub.2; SiR.sup.o.sub.3;
--(C.sub.1-4 straight or branched)alkylene)O--N(R.sup.o).sub.2; or
--(C.sub.1-4 straight or branched)alkylene)C(O)O--N(R.sup.o).sub.2,
wherein each R.sup.o may be substituted as defined below and is
independently hydrogen, C.sub.1-8 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, or sulfur, or, notwithstanding the
definition above, two independent occurrences of R.sup.o, taken
together with their intervening atom(s), form a 3-12-membered
saturated, partially unsaturated, or aryl mono- or polycyclic ring
having 0-4 heteroatoms independently selected from nitrogen,
oxygen, or sulfur, which may be substituted as defined below.
[0033] Suitable monovalent substituents on R.sup.o (or the ring
formed by taking two independent occurrences of R.sup.o together
with their intervening atoms), are independently halogen,
--(CH.sub.2).sub.0-2R.sup. , -(haloR.sup. ),
--(CH.sub.2).sub.0-2OH, --(CH.sub.2).sub.0-2OR.sup. ,
--(CH.sub.2).sub.0-2CH(OR.sup. ).sub.2; --O(haloR*), --CN,
--N.sub.3, --(CH.sub.2).sub.0-2C(O)R.sup. ,
--(CH.sub.2).sub.0-2C(O)OH, --(CH.sub.2).sub.0-2C(O)OR.sup. ,
--(CH.sub.2).sub.0-4C(O)N(R.sup.o).sub.2;
--(CH.sub.2).sub.0-2SR.sup. , --(CH.sub.2).sub.0-2SH,
--(CH.sub.2).sub.0-2NH.sub.2, --(CH.sub.2).sub.0-2NHR.sup. ,
--(CH.sub.2).sub.0-2NR.sup. .sub.2, --NO.sub.2, --SiR.sup. .sub.3,
--OSiR.sup. .sub.3, --C(O)SR.sup. , --(C.sub.1-4 straight or
branched alkylene)C(O)OR.sup. , or --SSR.sup. wherein each R.sup.
is unsubstituted or where preceded by "halo" is substituted only
with one or more halogens, and is independently selected from
C.sub.1-4 aliphatic, --CH.sub.2Ph, --O(CH.sub.2).sub.0-1Ph, or a
5-6-membered saturated, partially unsaturated, or aryl ring having
0-4 heteroatoms independently selected from nitrogen, oxygen, or
sulfur. Suitable divalent substituents on a saturated carbon atom
of R.sup.o include .dbd.O and .dbd.S.
[0034] Suitable divalent substituents on a saturated carbon atom of
an "optionally substituted" group include the following: .dbd.O,
.dbd.S, .dbd.NNR*.sub.2, .dbd.NNHC(O)R*, .dbd.NNHC(O)OR*,
.dbd.NNHS(O).sub.2R*, .dbd.NR*, .dbd.NOR*,
--O(C(R*.sub.2)).sub.2-3O--, or --S(C(R*.sub.2)).sub.2-3S--,
wherein each independent occurrence of R* is selected from
hydrogen, C.sub.1-6 aliphatic which may be substituted as defined
below, or an unsubstituted 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, or sulfur. Suitable divalent
substituents that are bound to vicinal substitutable carbons of an
"optionally substituted" group include: --O(CR*.sub.2).sub.2-3O--,
wherein each independent occurrence of R* is selected from
hydrogen, C.sub.1-6 aliphatic which may be substituted as defined
below, or an unsubstituted 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, or sulfur.
[0035] Suitable substituents on the aliphatic group of R* include
halogen, --R.sup. , --(haloR.sup. ), --OH, --OR.sup. ,
--O(haloR.sup. ), --CN, --C(O)OH, --C(O)OR.sup. , --NH.sub.2,
--NHR.sup. , --NR.sup. .sub.2, or --NO.sub.2, wherein each R.sup.
is unsubstituted or where preceded by "halo" is substituted only
with one or more halogens, and is independently C.sub.1-4
aliphatic, --CH.sub.2Ph, --O(CH.sub.2).sub.0-1Ph, or a 5-6-membered
saturated, partially unsaturated, or aryl ring having 0-4
heteroatoms independently selected from nitrogen, oxygen, or
sulfur.
[0036] Suitable substituents on a substitutable nitrogen of an
"optionally substituted" group include --R.sup..dagger.,
--NR.sup..dagger..sub.2, --C(O)R.sup..dagger.,
--C(O)OR.sup..dagger., --C(O)C(O)R.sup..dagger.,
--C(O)CH.sub.2C(O)R.sup..dagger., --S(O).sub.2R.sup..dagger.,
--S(O).sub.2NR.sup..dagger..sub.2, --C(S)NR.sup..dagger..sub.2,
--C(NH)NR.sup..dagger..sub.2, or
--N(R.sup..dagger.)S(O).sub.2R.sup..dagger.; wherein each
R.sup..dagger. is independently hydrogen, C.sub.1-6 aliphatic which
may be substituted as defined below, unsubstituted --OPh, or an
unsubstituted 5-6-membered saturated, partially unsaturated, or
aryl ring having 0-4 heteroatoms independently selected from
nitrogen, oxygen, or sulfur, or, notwithstanding the definition
above, two independent occurrences of R.sup..dagger., taken
together with their intervening atom(s) form an unsubstituted
3-12-membered saturated, partially unsaturated, or aryl mono- or
bicyclic ring having 0-4 heteroatoms independently selected from
nitrogen, oxygen, or sulfur. A substitutable nitrogen may be
substituted with three R.sup..dagger. substituents to provide a
charged ammonium moiety --N.sup.+(R.sup..dagger.).sub.3, wherein
the ammonium moiety is further complexed with a suitable
counterion.
[0037] Suitable substituents on the aliphatic group of
R.sup..dagger. are independently halogen, --R.sup. , -(haloR.sup.
), --OH, --OR.sup. , --O(haloR.sup. ), --CN, --C(O)OH,
--C(O)OR.sup. , --NH.sub.2, --NHR.sup. , --NR.sup. .sub.2, or
--NO.sub.2, wherein each R.sup. is unsubstituted or where preceded
by "halo" is substituted only with one or more halogens, and is
independently C.sub.1-4 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, or sulfur.
[0038] As used herein, the term "tautomer" includes two or more
interconvertable compounds resulting from at least one formal
migration of a hydrogen atom and at least one change in valency
(e.g., a single bond to a double bond, a triple bond to a single
bond, or vice versa). The exact ratio of the tautomers depends on
several factors, including temperature, solvent, and pH.
Tautomerizations (i.e., the reaction providing a tautomeric pair)
may catalyzed by acid or base. Exemplary tautomerizations include
keto-to-enol; amide-to-imide; lactam-to-lactim; enamine-to-imine;
and enamine-to-(a different) enamine tautomerizations.
[0039] As used herein, the term "isomers" includes any and all
geometric isomers and stereoisomers. For example, "isomers" include
cis- and trans-isomers, E- and Z-isomers, R- and S-enantiomers,
diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof,
and other mixtures thereof, as falling within the scope of the
disclosure. For instance, an isomer/enantiomer may, in some
embodiments, be provided substantially free of the corresponding
enantiomer, and may also be referred to as "optically enriched."
"Optically-enriched," as used herein, means that the compound is
made up of a significantly greater proportion of one enantiomer. In
certain embodiments the compound of the present disclosure is made
up of at least about 90% by weight of a preferred enantiomer. In
other embodiments the compound is made up of at least about 95%,
98%, or 99% by weight of a preferred enantiomer. Preferred
enantiomers may be isolated from racemic mixtures by any method
known to those skilled in the art, including chiral high pressure
liquid chromatography (HPLC) and the formation and crystallization
of chiral salts or prepared by asymmetric syntheses. See, for
example, Jacques, et al., Enantiomers, Racemates and Resolutions
(Wiley Interscience, New York, 1981); Wilen, S. H., et al.,
Tetrahedron 33:2725 (1977); Eliel, E. L. Stereochemistry of Carbon
Compounds (McGraw-Hill, NY, 1962); Wilen, S. H. Tables of Resolving
Agents and Optical Resolutions p. 268 (E. L. Eliel, Ed., Univ. of
Notre Dame Press, Notre Dame, Ind. 1972).
[0040] As used herein, "polymorph" refers to a crystalline
inventive compound existing in more than one crystalline
form/structure. When polymorphism exists as a result of difference
in crystal packing it is called packing polymorphism. Polymorphism
can also result from the existence of different conformers of the
same molecule in conformational polymorphism. In pseudopolymorphism
the different crystal types are the result of hydration or
solvation.
BRIEF DESCRIPTION OF THE FIGURES
[0041] FIGS. 1A-1B. .sup.1H NMR spectra (300 MHz) of PEC obtained
by catalyst 1 (FIG. 1A) and 4 (FIG. 1B) in conjunction with
[PPN]Cl.
[0042] FIG. 2. .sup.1H NMR spectra of PEC and PEO.
[0043] FIG. 3. (Salcy)CoOBzF.sub.5 induced ethylene oxide (EO)
polymerization in the presence of PPNCl. The catalytic activity is
strongly dependant on the PPNCl/Co ratio.
[0044] FIGS. 4A-4B. TGA (FIG. 4A) and DSC (FIG. 4B) analyses of
PEO-b-PEC.
DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS
[0045] As generally described above, the present disclosure
provides methods of synthesizing poly(ethylene carbonate)
compositions from ethylene oxide and carbon dioxide in the presence
of a metal complex. In certain embodiments, the poly(ethylene
carbonate) polymer is an alternating polymer. In certain
embodiments, the poly(ethylene carbonate) polymer is a tapered
co-polymer of polyethylene oxide and polyethylene carbonate. In
certain embodiments, the poly(ethylene carbonate) polymer is a
block co-polymer of polyethylene oxide and polyethylene
carbonate.
[0046] As is generally understood from the description as provided
herein, poly(ethylene carbonate) polymers of the present disclosure
encompass poly(ethylene carbonate) (PEC), as well as polymers which
comprise poly(ethylene carbonate), such as, for example,
polyethylene oxide-co-polyethylene carbonate.
[0047] The present disclosure also provides novel metal complexes
of the formula (I) as is described in detail below.
I. Metal Complexes
[0048] In certain embodiments, the metal complex is of the formula
(I):
##STR00004##
wherein:
[0049] M is a metal selected from zinc, cobalt, chromium, aluminum,
titanium, ruthenium and manganese;
[0050] X is absent or is a nucleophilic ligand;
[0051] each instance of R.sup.1, R.sup.2, and R.sup.3 is,
independently, selected from hydrogen, halogen, optionally
substituted aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, and optionally substituted heteroaryl,
or R.sup.1 and R.sup.2, or R.sup.2 and R.sup.3, are joined to form
an optionally substituted aryl or optionally substituted heteroaryl
ring; and
[0052] Ring A forms an optionally substituted 5- to 6-membered
ring.
[0053] In certain embodiments, the metal is aluminum. In certain
embodiments, the metal is chromium. In certain embodiments, the
metal is zinc. In certain embodiments, the metal is titanium. In
certain embodiments, the metal is ruthenium. In certain
embodiments, the metal is manganese. In certain embodiments, the
metal is cobalt. In certain embodiments, wherein the metal is
cobalt, the cobalt has a valency of +3 (i.e., Co(III)).
[0054] In certain embodiments, the metal complex is a metal
catalyst.
[0055] In certain embodiments, X is absent. However, in certain
embodiments, X is a nucleophilic ligand. Exemplary nucleophilic
ligands include, but are not limited to, --OR.sup.x, --SR.sup.X,
--O(C.dbd.O)R.sup.x, --O(C.dbd.O)OR.sup.x,
--O(C.dbd.O)N(R.sup.x).sub.2, --N(R.sup.x)(C.dbd.O)R.sup.x, --NC,
--CN, halo (e.g., --Br, --I, --Cl), --N.sub.3, --O(SO.sub.2)R.sup.x
and --OPR.sup.x.sub.3, wherein each R.sup.x is, independently,
selected from hydrogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted aryl
and optionally substituted heteroaryl.
[0056] In certain embodiments, X is --O(C.dbd.O)R.sup.x, wherein
R.sup.x is selected from optionally substituted aliphatic,
fluorinated aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, fluorinated aryl, and optionally
substituted heteroaryl.
[0057] For example, in certain embodiments, X is
--O(C.dbd.O)R.sup.x, wherein R.sup.x is optionally substituted
aliphatic. In certain embodiments, X is --O(C.dbd.O)R.sup.x,
wherein R.sup.x is optionally substituted alkyl and fluoroalkyl. In
certain embodiments, X is --O(C.dbd.O)CH.sub.3 or
--O(C.dbd.O)CF.sub.3.
[0058] Furthermore, in certain embodiments, X is
--O(C.dbd.O)R.sup.x, wherein R.sup.x is optionally substituted
aryl, fluoroaryl, or heteroaryl. In certain embodiments, X is
--O(C.dbd.O)R.sup.x, wherein R.sup.x is optionally substituted
aryl. In certain embodiments, X is --O(C.dbd.O)R.sup.x, wherein
R.sup.x is optionally substituted phenyl. In certain embodiments, X
is --O(C.dbd.O)C.sub.6H.sub.5 or --O(C.dbd.O)C.sub.6F.sub.5.
[0059] In certain embodiments, X is --OR.sup.x, wherein R.sup.x is
selected from optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl, and
optionally substituted heteroaryl.
[0060] For example, in certain embodiments, X is --OR.sup.x,
wherein R.sup.x is optionally substituted aryl. In certain
embodiments, X is --OR.sup.x, wherein R.sup.x is optionally
substituted phenyl. In certain embodiments, X is --OC.sub.6H.sub.5
or --OC.sub.6H.sub.2(2,4-NO.sub.2).
[0061] In certain embodiments, X is halo. In certain embodiments, X
is --Br. In certain embodiments, X is --Cl. In certain embodiments,
X is --I.
[0062] In certain embodiments, X is --O(SO.sub.2)R.sup.x. In
certain embodiments X is --OTs. In certain embodiments X is
--OSO.sub.2Me, In certain embodiments X is --OSO.sub.2CF.sub.3.
[0063] In certain embodiments, X is --N.sub.3.
[0064] In certain embodiments, X is --NC
[0065] In certain embodiments, X is --CN.
[0066] In certain embodiments, Ring A forms an optionally
substituted 5-membered ring. In certain embodiments, Ring A forms
an optionally substituted cyclopentyl ring. In certain embodiments,
Ring A forms an optionally substituted 5-membered aryl ring.
[0067] In certain embodiments, Ring A forms an optionally
substituted 6-membered ring. In certain embodiments, Ring A forms
an optionally substituted cyclohexyl ring. In certain embodiments,
Ring A forms an optionally substituted 6-membered aryl ring.
II. Northern and Southern Hemisphere of the Metal Complex
[0068] The metal complex of formula (I) may be considered in two
portions: a Northern Hemisphere comprising the imine nitrogen atoms
and Ring A, and Southern Hemisphere, comprising the rest of the
metal complex.
##STR00005##
Northern Hemisphere
[0069] As generally understood from the above, the Northern
Hemisphere of the metal complex is of the formula (i-a):
##STR00006##
[0070] wherein Ring A forms an optionally substituted 5- to
6-membered ring.
[0071] In certain embodiments, Ring A forms an optionally
substituted 6-membered ring of the formula (i-b):
##STR00007##
[0072] wherein R.sup.4A, R.sup.4B, R.sup.5A, R.sup.5B, and
R.sup.6A, R.sup.6B are, independently, selected from hydrogen,
halogen, optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl, and/or, R.sup.4A and R.sup.4B, and/or
R.sup.5A and R.sup.5B, and/or and R.sup.6A and R.sup.6B are
optionally joined to form an oxo (.dbd.O) group, an oxime
(.dbd.NOR.sup.a) group, an imine (.dbd.NN(R.sup.a).sub.2) group, an
alkenyl (.dbd.C(R.sup.b).sub.2) group, and/or a 3- to 6-membered
spirocyclic ring, wherein each instance of R.sup.a and R.sup.b is,
independently, hydrogen or optionally substituted aliphatic,
wherein optionally two R.sup.a groups or two R.sup.b groups are
joined to form a 3- to 6-membered ring.
[0073] In certain embodiments, R.sup.4A, R.sup.4B, R.sup.5A,
R.sup.5B, R.sup.6A, and R.sup.6B are, independently, selected from
hydrogen, optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, and optionally
substituted heteroaryl. In certain embodiments, R.sup.4A, R.sup.4B,
R.sup.5A, R.sup.5B, R.sup.6A, and R.sup.6B are, independently,
selected from hydrogen and optionally substituted aliphatic. In
certain embodiments, R.sup.4A, R.sup.4B, R.sup.5A, R.sup.5B,
R.sup.6A, and R.sup.6B are, independently, selected from hydrogen
and optionally substituted heteroaliphatic. In certain embodiments,
R.sup.4A, R.sup.4B, R.sup.5A, R.sup.5B, R.sup.6A, and R.sup.6B are
independently, selected from hydrogen and optionally substituted
aryl. In certain embodiments, R.sup.4A, R.sup.4B, R.sup.5A,
R.sup.5B, R.sup.6A, and R.sup.6B are, independently, selected from
hydrogen and optionally substituted heteroaryl. In certain
embodiments, two or more of R.sup.4A, R.sup.4B, R.sup.5A, R.sup.5B,
R.sup.6A, and R.sup.6B, are joined to form one or more aliphatic,
heteroaliphatic, aromatic, or heteroaromatic rings having 3 to 8
total ring atoms.
[0074] In certain embodiments, each of R.sup.4A, R.sup.4B,
R.sup.5A, R.sup.5B, R.sup.6A, and R.sup.6B are hydrogen.
[0075] For example, in certain embodiments of formula (i-b),
wherein each of R.sup.4A, R.sup.4B, R.sup.5A, R.sup.5B, R.sup.6A,
and R.sup.6B are hydrogen, Ring A forms a 6-membered ring of the
formula:
##STR00008##
[0076] In certain embodiments, Ring A forms an optionally
substituted 6-membered ring of the formula (i-c):
##STR00009##
[0077] wherein R.sup.5A and R.sup.5B are, independently, selected
from hydrogen, halogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl, and/or, R.sup.5A and
R.sup.5B are optionally joined to form an oxo (.dbd.O) group, an
oxime (.dbd.NOR.sup.a) group, an imine (.dbd.NN(R.sup.a).sub.2)
group, an alkenyl (.dbd.C(R.sup.b).sub.2) group, and/or a 3- to
6-membered spirocyclic ring, wherein each instance of R.sup.a and
R.sup.b is, independently, hydrogen or optionally substituted
aliphatic, wherein optionally two R.sup.a groups or two R.sup.b
groups are joined to form a 5- to 6-membered ring;
[0078] each instance of R.sup.12 is selected from hydrogen,
halogen, --OR.sup.c, --OC(.dbd.O)R.sup.c, --OC(.dbd.O)OR.sup.c,
--OC(.dbd.O)N(R.sup.d).sub.2, --OSO.sub.2R.sup.d,
--C(.dbd.O)OR.sup.c, --C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO,
--NCO, --N.sub.3, --NO2, --N(Rd)2, --N(R.sup.d)C(.dbd.O)R.sup.c,
--N(R.sup.d)C(.dbd.O)OR.sup.c, --N(R.sup.d)SO.sub.2R.sup.d,
--SO.sub.2R.sup.d, --SOR.sup.d, --SO.sub.2N(R.sup.d).sub.2,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl, wherein each instance of R.sup.c is,
independently, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl,
optionally substituted heteroaryl, and each instance of R.sup.d is,
independently, hydrogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl; and
[0079] c is 0 to 4.
[0080] In certain embodiments, R.sup.5A and R.sup.5B are,
independently, selected from hydrogen and optionally substituted
aliphatic. In certain embodiments, R.sup.5A and R.sup.5B are,
independently, selected from hydrogen and optionally substituted
heteroaliphatic. In certain embodiments, R.sup.5A and R.sup.5B are,
independently, selected from hydrogen and optionally substituted
aryl. In certain embodiments, R.sup.5A and R.sup.5B are,
independently, selected from hydrogen and optionally substituted
heteroaryl.
[0081] However, in certain embodiments, each R.sup.5A and R.sup.5B
is hydrogen.
[0082] In certain embodiments, c is 0 to 2. In certain embodiments,
c is 0 to 1. In certain embodiments, c is 0. In certain
embodiments, c is 1.
[0083] In certain embodiments, each instance of R.sup.12 is,
independently, selected from hydrogen and optionally substituted
aliphatic. In certain embodiments, each instance of R.sup.12 is,
independently, selected from hydrogen and optionally substituted
heteroaliphatic. In certain embodiments, each instance of R.sup.12
is, independently, selected from hydrogen and optionally
substituted aryl. In certain embodiments, each instance of R.sup.12
is, independently, selected from hydrogen and optionally
substituted heteroaryl.
[0084] However, in certain embodiments, each instance of R.sup.12
is hydrogen.
[0085] In certain embodiments, Ring A forms an optionally
substituted 5-membered ring of the formula (I-d):
##STR00010##
[0086] wherein R.sup.4A, R.sup.4B, R.sup.5A, and R.sup.5B are,
independently, selected from hydrogen, halogen, optionally
substituted aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, optionally substituted heteroaryl,
and/or, R.sup.4A and R.sup.4B and/or R.sup.5A and R.sup.5B are
optionally joined to form an oxo (.dbd.O) group, an oxime
(.dbd.NOR.sup.a) group, an imine (.dbd.NN(R.sup.a).sub.2) group, an
alkenyl (.dbd.C(R.sup.b).sub.2) group, and/or a 3- to 6-membered
spirocyclic ring, wherein each instance of R.sup.a and R.sup.b is,
independently, hydrogen or optionally substituted aliphatic,
wherein optionally two R.sup.a groups or two R.sup.b groups are
joined to form a 5- to 6-membered ring.
[0087] In certain embodiments, wherein R.sup.4A, R.sup.4B,
R.sup.5A, and R.sup.5B are, independently, selected from hydrogen,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl, or wherein one of R.sup.4A, R.sup.4B,
R.sup.5A, and R.sup.5B and one of R.sup.4A, R.sup.4B, R.sup.5A, and
R.sup.5B are optionally joined to form a 3- to 7-membered ring.
[0088] In certain embodiments, R.sup.4A, R.sup.4B, R.sup.5A, and
R.sup.5B are, independently, selected from hydrogen and optionally
substituted aliphatic. In certain embodiments, R.sup.4A, R.sup.4B,
R.sup.5A, and R.sup.5B are, independently, selected from hydrogen
and optionally substituted heteroaliphatic. In certain embodiments,
R.sup.4A, R.sup.4B, R.sup.5A, and R.sup.5B are, independently,
selected from hydrogen and optionally substituted aryl. In certain
embodiments, R.sup.4A, R.sup.4B, R.sup.5A, and R.sup.5B are,
independently, selected from hydrogen and optionally substituted
heteroaryl. In certain embodiments, one of R.sup.4A, R.sup.4B,
R.sup.5A, and R.sup.5B and one of R.sup.4A, R.sup.4B, R.sup.5A, and
R.sup.5B are optionally joined to form a 3- to 6-membered ring.
[0089] However, in certain embodiments, each instance of R.sup.4A,
R.sup.4B, R.sup.5A, and R.sup.5B is hydrogen.
[0090] For example, in certain embodiments of formula (I-d),
wherein R.sup.4A, R.sup.4B, R.sup.5A, and R.sup.5B are each
hydrogen, Ring A forms a 5-membered ring of the formula:
##STR00011##
[0091] In certain embodiments of formula (I-d), wherein R.sup.4B
and R.sup.5B are joined to form an optionally substituted
6-membered ring, Ring A forms an optionally substituted 5-membered
ring of the formula (i-f):
##STR00012##
[0092] R.sup.4A, R.sup.5A, R.sup.13A, R.sup.13B, R.sup.14A,
R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A, R.sup.16B are,
independently, selected from hydrogen, halogen, --OR.sup.c,
--OC(.dbd.O)R.sup.c, --OC(.dbd.O)OR.sup.c,
--OC(.dbd.O)N(R.sup.d).sub.2, --OSO.sub.2R.sup.d,
--C(.dbd.O)OR.sup.c, --C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO,
--NCO, --N.sub.3, --NO2, --N(Rd)2, --N(R.sup.d)C(.dbd.O)OR.sup.c,
--N(R.sup.d)C(.dbd.O)R.sup.c, --N(R.sup.d)SO.sub.2R.sup.d,
--SO.sub.2R.sup.d, --SOR.sup.d, --SO.sub.2N(R.sup.d).sub.2,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl; and/or, optionally, R.sup.13A and
R.sup.13B, and/or R.sup.14A and R.sup.14B, and/or R.sup.15A and
R.sup.15B, and/or R.sup.16A and R.sup.16B are optionally joined to
form an oxo (.dbd.O) group, an oxime (.dbd.NOR.sup.a) group, an
imine (.dbd.NN(R.sup.a).sub.2) group, an alkenyl
(.dbd.C(R.sup.b).sub.2) group, and/or a 3- to 6-membered
spirocyclic ring, wherein each instance of R.sup.a and R.sup.b is,
independently, hydrogen or optionally substituted aliphatic,
wherein optionally two R.sup.a groups or two R.sup.b groups are
joined to form a 3- to 6-membered ring.
[0093] In certain embodiments, R.sup.4A, R.sup.5A, R.sup.13A,
R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A,
R.sup.16B are, independently, selected from hydrogen, halogen,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl. In certain embodiments, R.sup.4A, R.sup.5A,
R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B,
R.sup.16A, R.sup.16B are independently, selected from hydrogen and
optionally substituted aliphatic. In certain embodiments, R.sup.4A,
R.sup.5A, R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A,
R.sup.15B, R.sup.16A, R.sup.16B are, independently, selected from
hydrogen and optionally substituted heteroaliphatic. In certain
embodiments, R.sup.4A, R.sup.5A, R.sup.13A, R.sup.13B, R.sup.14A,
R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A, R.sup.16B are,
independently, selected from hydrogen and optionally substituted
aryl. In certain embodiments, R.sup.4A, R.sup.5A, R.sup.13A,
R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A,
R.sup.16B are, independently, selected from hydrogen and optionally
substituted heteroaryl.
[0094] However, in certain embodiments, each of R.sup.4A, R.sup.5A,
R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B,
R.sup.16A, R.sup.16B is hydrogen.
[0095] For example, in certain embodiments of formula (I-d),
wherein R.sup.4B and R.sup.5B are joined to form an optionally
substituted 6-membered ring and each of R.sup.4A, R.sup.5A,
R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B,
R.sup.16A, R.sup.16B is hydrogen, Ring A forms an optionally
substituted 5-membered ring of the formula (i-g):
##STR00013##
[0096] In certain embodiments of formula (I-d), wherein R.sup.4B
and R.sup.5B are joined to form an optionally substituted
6-membered ring, Ring A forms an optionally substituted 5-membered
ring of any of the formulae (i-h) to (i-k):
##STR00014##
[0097] or a mixture thereof;
[0098] wherein R.sup.4A, R.sup.5A, R.sup.13A, R.sup.13B, R.sup.14A,
R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A, R.sup.16B are,
independently, selected from hydrogen, halogen, --OR.sup.c,
--OC(.dbd.O)R.sup.c, --OC(.dbd.O)OR.sup.c,
--OC(.dbd.O)N(R.sup.d).sub.2, --OSO.sub.2R.sup.d,
--C(.dbd.O)OR.sup.c, --C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO,
--NCO, --N.sub.3, --NO.sub.2, --N(Rd)2,
--N(R.sup.d)C(.dbd.O)OR.sup.c, --N(R.sup.d)C(.dbd.O)R.sup.c,
--N(R.sup.d)SO.sub.2R.sup.d, --SO.sub.2R.sup.d, --SOR.sup.B,
--SO.sub.2N(R.sup.d).sub.2, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl, and/or, R.sup.13A and
R.sup.13B, and/or R.sup.14A and R.sup.14B, and/or R.sup.15A and
R.sup.15B, and/or R.sup.16A and R.sup.16B are optionally joined to
form an oxo (.dbd.O) group, an oxime (.dbd.NOR.sup.a) group, an
imine (.dbd.NN(R.sup.a).sub.2) group, an alkenyl
(.dbd.C(R.sup.b).sub.2) group, and/or a 3- to 6-membered
spirocyclic ring, wherein each instance of R.sup.a and R.sup.b is,
independently, hydrogen or optionally substituted aliphatic,
wherein optionally two R.sup.a groups or two R.sup.b groups are
joined to form a 5- to 6-membered ring.
[0099] In certain embodiments of formulae (i-h) to (i-k), wherein
R.sup.4B and R.sup.5B are joined to form an optionally substituted
6-membered ring, and R.sup.4A, R.sup.5A, R.sup.13A, R.sup.13B,
R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A, R.sup.16B
are each hydrogen, Ring A forms an optionally substituted
5-membered ring of any of the formulae (i-l) to (i-o):
##STR00015##
[0100] or any mixture thereof.
[0101] In certain embodiments of formula (I-d), wherein R.sup.4B
and R.sup.5B are joined to form an optionally substituted
6-membered ring, Ring A forms an optionally substituted 5-membered
ring of the formula (i-p):
##STR00016##
[0102] wherein each instance of R.sup.17 is, independently,
selected from hydrogen, halogen, --OR.sup.c, --OC(.dbd.O)R.sup.c,
--OC(.dbd.O)OR.sup.c, --OC(.dbd.O)N(R.sup.d).sub.2,
--OSO.sub.2R.sup.d, --C(.dbd.O)OR.sup.c,
--C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO, --NCO, --N.sub.3,
--NO.sub.2, --N(R.sup.d).sub.2, --N(R.sup.d)C(.dbd.O)OR.sup.c,
--N(R.sup.d)C(.dbd.O)R.sup.c, --N(R.sup.d)SO.sub.2R.sup.d,
--SO.sub.2R.sup.d, --SOR.sup.B, --SO.sub.2N(R.sup.d).sub.2,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl, wherein each instance of R.sup.c is,
independently, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl,
optionally substituted heteroaryl, and each instance of R.sup.d is,
independently, hydrogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl; and/or two R.sup.17 groups
adjacent to each other are joined to form an optionally substituted
5- to 6-membered ring; and
[0103] d is 0 to 4.
[0104] In certain embodiments, d is 0 to 2. In certain embodiments,
d is 0 to 1. In certain embodiments, d is 0. In certain
embodiments, d is 1.
[0105] In certain embodiments, each instance of R.sup.17 is,
independently, selected from hydrogen, optionally substituted
aliphatic, optionally substituted heteroaliphatic, optionally
substituted aryl, and optionally substituted heteroaryl. In certain
embodiments, each instance of R.sup.17 is, independently, selected
from hydrogen and optionally substituted aliphatic. In certain
embodiments, each instance of R.sup.17 is, independently, selected
from hydrogen and optionally substituted heteroaliphatic. In
certain embodiments, each instance of R.sup.17 is, independently,
selected from hydrogen and optionally substituted aryl. In certain
embodiments, each instance of R.sup.17 is, independently, selected
from hydrogen and optionally substituted heteroaryl.
[0106] However, in certain embodiments, each instance of R.sup.17
is hydrogen.
[0107] For example, in certain embodiments of formula (i-p),
wherein R.sup.4B and R.sup.5B are joined to form an optionally
substituted 6-membered ring, Ring A forms an optionally substituted
5-membered ring of the formula (i-q):
##STR00017##
Southern Hemisphere
[0108] As generally understood from the above, the Southern
Hemisphere of the metal complex is of the formula (ii-a):
##STR00018##
[0109] wherein M and X are as defined above and herein, and
[0110] each instance of R.sup.1, R.sup.2, and R.sup.3 is,
independently, selected from hydrogen, halogen, --OR.sup.c,
--OC(.dbd.O)R.sup.c, --OC(.dbd.O)OR.sup.c,
--OC(.dbd.O)N(R.sup.d).sub.2, --OSO.sub.2R.sup.d,
--C(.dbd.O)OR.sup.c, --C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO,
--NCO, --N.sub.3, --NO.sub.2, --N(R.sup.d).sub.2,
--N(R.sup.d)C(.dbd.O)OR.sup.c, --N(R.sup.d)C(.dbd.O)R.sup.c,
--N(R.sup.d)SO.sub.2R.sup.d, --SO.sub.2R.sup.d, --SOR.sup.B,
--SO.sub.2N(R.sup.d).sub.2, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, and optionally substituted heteroaryl, and/or any of R.sup.1
and R.sup.2, and/or any of R.sup.2 and R.sup.3, are joined to form
an optionally substituted aryl or optionally substituted heteroaryl
ring.
[0111] In certain embodiments, R.sup.1 is hydrogen, halogen,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, or optionally
substituted heteroaryl. In certain embodiments, each instance of
R.sup.1 is hydrogen. In certain embodiments, each instance of
R.sup.1 is halogen. In certain embodiments, each instance of
R.sup.1 is optionally substituted aliphatic. In certain
embodiments, each instance of R.sup.1 is optionally substituted
heteroaliphatic. In certain embodiments, each instance of R.sup.1
is optionally substituted aryl. In certain embodiments, each
instance of R.sup.1 is optionally substituted heteroaryl.
[0112] In certain embodiments, each instance of R.sup.2 is
hydrogen, halogen, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl, or
optionally substituted heteroaryl. In certain embodiments, each
instance of R.sup.2 is hydrogen. In certain embodiments, each
instance of R.sup.2 is halogen. In certain embodiments, each
instance of R.sup.2 is optionally substituted aliphatic. In certain
embodiments, each instance of R.sup.2 is optionally substituted
heteroaliphatic. In certain embodiments, each instance of R.sup.2
is optionally substituted aryl. In certain embodiments, each
instance of R.sup.2 is optionally substituted heteroaryl.
[0113] In certain embodiments, each instance of R.sup.3 is
hydrogen, halogen, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl, or
optionally substituted heteroaryl. In certain embodiments, each
instance of R.sup.3 is hydrogen. In certain embodiments, each
instance of R.sup.3 is halogen. In certain embodiments, each
instance of R.sup.3 is optionally substituted aliphatic. In certain
embodiments, each instance of R.sup.3 is optionally substituted
heteroaliphatic. In certain embodiments, each instance of R.sup.3
is optionally substituted aryl. In certain embodiments, each
instance of R.sup.3 is optionally substituted heteroaryl.
[0114] However, in certain embodiments, R.sup.1 and R.sup.2 are
joined to form an optionally substituted aryl or optionally
substituted heteroaryl ring. In certain embodiments, R.sup.1 and
R.sup.2 are joined to form an optionally substituted aryl ring. In
certain embodiments, R.sup.1 and R.sup.2 are joined to form an
optionally substituted heteroaryl ring.
[0115] In other embodiments, R.sup.2 and R.sup.3 are joined to form
an optionally substituted aryl or optionally substituted heteroaryl
ring. In certain embodiments, R.sup.2 and R.sup.3 are joined to
form an optionally substituted aryl ring. In certain embodiments,
R.sup.2 and R.sup.3 are joined to form an optionally substituted
heteroaryl ring.
[0116] In certain embodiments, each instance of R.sup.1, R.sup.2,
and R.sup.3 is, independently, selected from hydrogen, optionally
substituted aliphatic, and/or any of R.sup.1 and R.sup.2, and/or
any of R.sup.2 and R.sup.3, are joined to form an optionally
substituted aryl or optionally substituted heteroaryl ring. In
certain embodiments, each instance of R.sup.1, R.sup.2, and R.sup.3
is, independently, selected from hydrogen and/or any of R.sup.1 and
R.sup.2 are joined to form an optionally substituted aryl or
optionally substituted heteroaryl ring. In certain embodiments,
each instance of R.sup.1, R.sup.2, and R.sup.3 is, independently,
selected from hydrogen and/or any of R.sup.2 and R.sup.3, are
joined to form an optionally substituted aryl or optionally
substituted heteroaryl ring.
[0117] In certain embodiments, each instance of R.sup.1, R.sup.2,
and R.sup.3 is, independently, selected from hydrogen and
optionally substituted aliphatic. In certain embodiments, each
instance of R.sup.1, R.sup.2, and R.sup.3 is, independently,
selected from hydrogen and optionally substituted heteroaliphatic.
In certain embodiments, each instance of R.sup.1, R.sup.2, and
R.sup.3 is, independently, selected from hydrogen and optionally
substituted aryl. In certain embodiments, each instance of R.sup.1,
R.sup.2, and R.sup.3 is, independently, selected from hydrogen and
optionally substituted heteroaryl.
[0118] However, in certain embodiments, each instance of R.sup.1,
R.sup.2, and R.sup.3 is hydrogen. In certain embodiments, each
instance of R.sup.1 and R.sup.3 is hydrogen. In certain
embodiments, each instance of R.sup.2 and R.sup.3 is hydrogen. In
certain embodiments, each instance of R.sup.1 and R.sup.2 is
hydrogen. In certain embodiments, each instance of R.sup.1 is
hydrogen. In certain embodiments, each instance of R.sup.2 is
hydrogen. In certain embodiments, each instance of R.sup.3 is
hydrogen.
[0119] In certain embodiments, wherein R.sup.1 is an optionally
substituted aryl moiety, the Southern Hemisphere of the metal
complex is of the formula (ii-b):
##STR00019##
[0120] wherein M, X, R.sup.2 and R.sup.3 are as defined above and
herein;
[0121] each instance of R.sup.11 is, independently, selected from
hydrogen, halogen, --OR.sup.c, --OC(.dbd.O)R.sup.c,
--OC(.dbd.O)OR.sup.c, --OC(.dbd.O)N(R.sup.d).sub.2,
--OSO.sub.2R.sup.d, --C(.dbd.O)OR.sup.c,
--C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO, --NCO, --N.sub.3,
--NO.sub.2, --N(R.sup.d).sub.2, --N(R.sup.d)C(.dbd.O)OR.sup.c,
--N(R.sup.d)C(.dbd.O)R.sup.c, --N(R.sup.d)SO.sub.2R.sup.d,
--SO.sub.2R.sup.d, --SOR.sup.d, --SO.sub.2N(R.sup.d).sub.2,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl, wherein each instance of R.sup.c is,
independently, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl,
optionally substituted heteroaryl, and each instance of R.sup.d is,
independently, hydrogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl; and/or two R.sup.11 groups
adjacent to each other are joined to form an optionally substituted
5- to 6-membered ring; and
[0122] b is 0 to 5.
[0123] In certain embodiments, b is 0 to 2. In certain embodiments,
b is 0 to 1. In certain embodiments, b is 0. In certain
embodiments, b is 1.
[0124] In certain embodiments, each instance of R.sup.11 is,
independently, selected from hydrogen, optionally substituted
aliphatic, optionally substituted heteroaliphatic, optionally
substituted aryl, and optionally substituted heteroaryl, and/or two
R.sup.11 groups adjacent to each other are joined to form an
optionally substituted 5- to 6-membered ring. In certain
embodiments, each instance of R.sup.11 is, independently, selected
from hydrogen and optionally substituted aliphatic. In certain
embodiments, each instance of R.sup.11 is, independently, selected
from hydrogen, optionally substituted heteroaliphatic. In certain
embodiments, each instance of R.sup.11 is, independently, selected
from hydrogen, optionally substituted aryl. In certain embodiments,
each instance of R.sup.11 is, independently, selected from
hydrogen, optionally substituted heteroaryl.
[0125] However, in certain embodiments, each instance of R.sup.11
is hydrogen.
[0126] In certain embodiments, wherein one of R.sup.1 and R.sup.2
are joined to form an optionally substituted aryl ring, the
Southern Hemisphere of the metal complex is of the formula
(ii-c):
##STR00020##
[0127] wherein M, X, R.sup.1, R.sup.2 and R.sup.3 are, as defined
above and herein; and
[0128] R.sup.7, R.sup.8, R.sup.9, and R.sup.10, are, independently,
selected from hydrogen, halogen, --OR.sup.c, --OC(.dbd.O)R.sup.c,
--OC(.dbd.O)OR.sup.c, --OC(.dbd.O)N(R.sup.d).sub.2,
--OSO.sub.2R.sup.d, --C(.dbd.O)OR.sup.c,
--C(.dbd.O)N(R.sup.d).sub.2, --CN, --CNO, --NCO, --N.sub.3,
--NO.sub.2, --N(R.sup.d).sub.2, --N(R.sup.d)C(.dbd.O)OR.sup.c,
--N(R.sup.d)C(.dbd.O)R.sup.c, --N(R.sup.d)SO.sub.2R.sup.d,
--SO.sub.2R.sup.d, --SOR.sup.d, --SO.sub.2N(R.sup.d).sub.2,
optionally substituted aliphatic, optionally substituted
heteroaliphatic, optionally substituted aryl, optionally
substituted heteroaryl, wherein each instance of R.sup.c is,
independently, optionally substituted aliphatic, optionally
substituted heteroaliphatic, optionally substituted aryl,
optionally substituted heteroaryl, and each instance of R.sup.d is,
independently, hydrogen, optionally substituted aliphatic,
optionally substituted heteroaliphatic, optionally substituted
aryl, optionally substituted heteroaryl; and/or two groups selected
from R.sup.7, R.sup.8, R.sup.9, and R.sup.10 adjacent to each other
are joined to form an optionally substituted 5- to 6-membered
ring.
[0129] In certain embodiments, R.sup.7, R.sup.8, R.sup.9, and
R.sup.10 are, independently, selected from hydrogen, optionally
substituted aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, and optionally substituted heteroaryl,
and/or two groups selected from R.sup.7, R.sup.8, R.sup.9, and
R.sup.10 adjacent to each other are joined to form an optionally
substituted 5- to 7-membered ring. In certain embodiments, R.sup.7,
R.sup.8, R.sup.9, and R.sup.10 are, independently, selected from
hydrogen and optionally substituted aliphatic. In certain
embodiments, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are,
independently, selected from hydrogen and optionally substituted
heteroaliphatic. In certain embodiments, R.sup.7, R.sup.8, R.sup.9,
and R.sup.10 are, independently, selected from hydrogen and
optionally substituted aryl. In certain embodiments, R.sup.7,
R.sup.8, R.sup.9, and R.sup.10 are, independently, selected from
hydrogen and optionally substituted heteroaryl.
[0130] In certain embodiments, R.sup.7, R.sup.8, R.sup.9, and
R.sup.10 are, independently, selected from hydrogen and optionally
substituted aryl. In certain embodiments, R.sup.7, R.sup.8,
R.sup.9, and R.sup.10 are, independently, selected from hydrogen
and optionally substituted phenyl.
[0131] In certain embodiments, R.sup.7, R.sup.8, R.sup.9, and
R.sup.10 are, independently, selected from hydrogen and optionally
substituted C.sub.1-10 aliphatic. In certain embodiments, R.sup.7,
R.sup.8, R.sup.9, and R.sup.10 are, independently, selected from
hydrogen and optionally substituted C.sub.1-10 alkyl. In certain
embodiments, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are,
independently, selected from hydrogen and methyl, trichloromethyl,
trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl,
iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl,
benzyl and cumyl.
[0132] However, in certain embodiments, each of R.sup.7, R.sup.8,
R.sup.9, and R.sup.10 are hydrogen. In certain embodiments, each of
R.sup.8 and R.sup.10 are hydrogen. In certain embodiments, R.sup.8
is hydrogen. In certain embodiments, R.sup.10 is hydrogen.
[0133] For example, in certain embodiments of the formula (ii-c),
wherein R.sup.8 and R.sup.10 are hydrogen, the Southern Hemisphere
of the metal complex is of the formula (ii-d):
##STR00021##
[0134] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7 and R.sup.9
are, as defined above and herein.
[0135] In certain embodiments, of the formula (ii-d), wherein both
R.sup.1 and R.sup.2 groups are joined to form an optionally
substituted aryl ring, the Southern Hemisphere of the metal complex
is of the formula (ii-dd):
##STR00022##
wherein M, X, R.sup.3, R.sup.7 and R.sup.9 are, as defined above
and herein.
[0136] In certain embodiments, each occurrence of R.sup.3 is,
independently, selected from hydrogen, halogen, optionally
substituted aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, and optionally substituted heteroaryl.
In certain embodiments, each occurrence of R.sup.3 is hydrogen.
[0137] In certain embodiments, each occurrence of R.sup.7 and
R.sup.9 is independently selected from hydrogen, optionally
substituted aliphatic, optionally substituted heteroaliphatic,
optionally substituted aryl, and optionally substituted
heteroaryl.
[0138] In certain embodiments, each occurrence of R.sup.7 and
R.sup.9 is independently selected from hydrogen, optionally
substituted aliphatic and optionally substituted aryl.
[0139] In certain embodiments, each occurrence of R.sup.7 is the
same. In certain embodiments, each occurrence of R.sup.9 is the
same. In certain embodiments, each occurrence of R.sup.7 is the
same and each occurrence of R.sup.9 is the same. In certain
embodiments, R.sup.7 and R.sup.9 are different.
[0140] In certain embodiments, each occurrence of R.sup.7 and
R.sup.9 is independently selected from hydrogen and optionally
substituted C.sub.1-12 aliphatic. In certain embodiments, each
occurrence of R.sup.7 and R.sup.9 is independently selected from
hydrogen and optionally substituted C.sub.1-12 alkyl. In certain
embodiments, each occurrence of R.sup.7 and R.sup.9 is
independently selected from hydrogen, methyl, trichloromethyl,
trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl,
iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl,
benzyl and cumyl.
[0141] In some embodiments R.sup.7 is hydrogen. In some embodiments
R.sup.7 is methyl. In some embodiments R.sup.7 is trichloromethyl.
In some embodiments R.sup.7 is trifluoromethyl. In some embodiments
R.sup.7 is ethyl. In some embodiments R.sup.7 is n-propyl. In some
embodiments R.sup.7 is isopropyl. In some embodiments R.sup.7 is
t-butyl. In some embodiments R.sup.7 is sec-butyl. In some
embodiments R.sup.7 is iso-butyl. In some embodiments R.sup.7 is
n-pentyl. In some embodiments R.sup.7 is neopentyl. In some
embodiments R.sup.7 is amyl. In some embodiments R.sup.7 is trityl.
In some embodiments R.sup.7 is adamantyl. In some embodiments
R.sup.7 is thexyl. In some embodiments R.sup.7 is benzyl. In some
embodiments R.sup.7 is cumyl.
[0142] In some embodiments R.sup.9 is hydrogen. In some embodiments
R.sup.9 is methyl. In some embodiments R.sup.9 is trichloromethyl.
In some embodiments R.sup.9 is trifluoromethyl. In some embodiments
R.sup.9 is ethyl. In some embodiments R.sup.9 is n-propyl. In some
embodiments R.sup.9 is isopropyl. In some embodiments R.sup.9 is
t-butyl. In some embodiments R.sup.9 is sec-butyl. In some
embodiments R.sup.9 is iso-butyl. In some embodiments R.sup.9 is
n-pentyl. In some embodiments R.sup.9 is neopentyl. In some
embodiments R.sup.9 is amyl. In some embodiments R.sup.9 is trityl.
In some embodiments R.sup.9 is adamantyl. In some embodiments
R.sup.9 is thexyl. In some embodiments R.sup.9 is benzyl. In some
embodiments R.sup.9 is cumyl.
[0143] In certain embodiments, each occurrence of R.sup.7 and
R.sup.9 is independently selected from hydrogen and optionally
substituted aryl. In certain embodiments, each occurrence of
R.sup.7 and R.sup.9 is independently selected from hydrogen and
optionally substituted phenyl.
[0144] Without wishing to be bound by any theory, it is believed
that the relative sizes of the R.sup.7 and R.sup.9 groups influence
the rate and selectivity of the polymerization reactions catalyzed
by the metal complexes In certain embodiments it is advantageous
for there to be a difference in the sizes of R.sup.7 and R.sup.9.
In certain embodiments, the group R.sup.7 is larger than the group
R.sup.9. However, in certain embodiments, the group R.sup.9 is
larger than the group R.sup.7.
[0145] The relative size of a group (e.g., in this instance,
R.sup.7 to R.sup.9) can be determined from the van der Waals
surface and/or molecular volume as calculated for that group. For a
single molecule (i.e., a molecule for which there is a path between
any two atoms along covalent bonds), the van der Waals surface is a
closed surface, and hence, it contains volume. This volume is
called the molecular volume, or van der Waals volume, and is
usually given in A.sup.3. The straightforward way of calculating
molecular volume on the computer is by numerical integration, i.e.,
by surrounding the van der Waals envelope with a grid of small
bricks and summing up the bricks whose centers are within the van
der Waals envelope of the molecule (i.e., are within a van der
Waals radius from atom nucleus) (see, for example, Whitley, "Van
der Waals surface graphs and molecular shape," Journal of
Mathematical Chemistry (1998) 23:377-397).
[0146] The relative size of a group can also be measured from the
"A-value" for a given group. The A-value is a measure of the
effective size of a given group. The "A-value" refers to the
conformational energies (-G.sup.0 values) as determined for a
substituted cyclohexane and the relative axial-equatorial
disposition of the substituent (see Table 1, provided below, and
pages 695-697 of Eliel and Wilen, Chapter 11 entitled
"Configuration and Confirmation of Cyclic Molecules" of
Stereochemistry of Organic Compounds, John Wiley & Sons, Inc.,
New York: 1994, incorporated herein by reference). More detailed
tabulations have been compiled by Hirsch, "Table of Conformational
Energies", Top. Stereochem. (1967) 1:199; Jensen and Bushweller,
"Conformational Preferences in Cyclohexanes and Cyclohexenes", Adv.
Alicycl. Chem. (1971) 3:139; and Schnieder and Hoppen "Carbon-13
Nuclear Magnetic Resonance Substituent-induced Shieldings and
Conformational Equilibria in Cyclohexanes", J. Org. Chem. (1978)
43:3866; the entirety of each of which is incorporated herein by
reference.
TABLE-US-00001 TABLE 1 Exemplary A - values -G.sup.0 value Group
kcal/mol kJ/mol --H ~0 ~0 --D 0.0006 0.025 --T 0.011 0.046 --F
0.25-0.42 1.05-1.75 --Cl 0.53-0.64 2.22-2.68 --Br 0.48-0.67
2.01-2.80 --I 0.47-0.61 1.97-2.55 --OtBu 0.75 3.14 --OPh 0.65 2.72
--OC(.dbd.O)CH.sub.3 0.68-0.87 2.85-3.64 --OSi(CH.sub.3).sub.3 0.74
3.10 --NO.sub.2 1.1 4.8 --P(CH.sub.3).sub.2 1.5-1.6 6.3-6.7
--P(Ph).sub.2 1.8 7.5 --C(.dbd.O)CH.sub.3 1.02-1.52 4.27-6.36
--C(.dbd.O)OCH.sub.3 1.2-1.3 5.0-5.4 --C(.dbd.O)OCH.sub.2CH.sub.3
1.1-1.2 4.6-5.0 --CN 0.2 0.84 --CCH 0.41-0.52 1.71-2.18
--CHCH.sub.2 1.49-1.68 6.23-7.0 --CH.sub.3(--Me) 1.74 7.28
--CH.sub.2CH.sub.3(--Et) 1.79 7.49 --CH(CH.sub.3).sub.2(--iPr) 2.21
9.25 --C(CH.sub.3).sub.3(--tBu) 4.7-4.9 19.7-20.5 --CH.sub.2Ph 1.68
7.03 --Ph 2.8 11.71 --Si(CH.sub.3).sub.3 2.5 10.5 --C.sub.6H.sub.11
2.2 9.2 --CF.sub.3 2.4-2.5 10.0-10.5
[0147] Thus, in certain embodiments, the molecular volume of group
R.sup.7 is larger than the molecular volume of group R.sup.9. In
certain embodiments, the molecular volume of R.sup.7 is at least
1.2 times greater than the molecular volume of R.sup.9. In certain
embodiments, the molecular volume of R.sup.7 is at least 1.5 times
greater than the molecular volume of R.sup.9. In certain
embodiments, the molecular volume of R.sup.7 is at least 1.8 times
greater than the molecular volume of R.sup.9. In certain
embodiments, the molecular volume of R.sup.7 is at least 2 times
greater than the molecular volume of R.sup.9. In certain
embodiments, the molecular volume of R.sup.7 is at least 2.5 times
greater than the molecular volume of R.sup.9. In certain
embodiments, the molecular volume of R.sup.7 is at least 3 times
greater than the molecular volume of R.sup.9.
[0148] However, in certain embodiments, the molecular volume of
group R.sup.9 is larger than the molecular volume of group R.sup.7.
In certain embodiments, the molecular volume of R.sup.9 is at least
1.2 times greater than the molecular volume of R.sup.7. In certain
embodiments, the molecular volume of R.sup.9 is at least 1.5 times
greater than the molecular volume of R.sup.7. In certain
embodiments, the molecular volume of R.sup.9 is at least 1.8 times
greater than the molecular volume of R.sup.7. In certain
embodiments, the molecular volume of R.sup.9 is at least 2 times
greater than the molecular volume of R.sup.7. In certain
embodiments, the molecular volume of R.sup.9 is at least 2.5 times
greater than the molecular volume of R.sup.7. In certain
embodiments, the molecular volume of R.sup.9 is at least 3 times
greater than the molecular volume of R.sup.7.
[0149] In certain embodiments, the molecular volume of R.sup.7 is
greater than the molecular volume of R.sup.9. In certain
embodiments, the A-value of R.sup.7 is at least 1.2 times greater
than the A value of R.sup.9. In certain embodiments, the A-value of
R.sup.7 is at least 1.5 times greater than the A value of R.sup.9.
In certain embodiments, the A-value of R.sup.7 is at least 1.8
times greater than the A value of R.sup.9. In certain embodiments,
the A-value of R.sup.7 is at least 2 times greater than the A value
of R.sup.9. In certain embodiments, the A-value of R.sup.7 is at
least 2.5 times greater than the A value of R.sup.9. In certain
embodiments, the A-value of R.sup.7 is at least 3 times greater
than the A value of R.sup.9.
[0150] However, in certain embodiments, the A-value of R.sup.9 is
greater than the A-value of R.sup.7. In certain embodiments, the
A-value of R.sup.9 is at least 1.2 times greater than the A value
of R.sup.7. In certain embodiments, the A-value of R.sup.9 is at
least 1.5 times greater than the A value of R.sup.7. In certain
embodiments, the A-value of R.sup.9 is at least 1.8 times greater
than the A value of R.sup.7. In certain embodiments, the A-value of
R.sup.9 is at least 2 times greater than the A value of R.sup.7. In
certain embodiments, the A-value of R.sup.9 is at least 2.5 times
greater than the A value of R.sup.7. In certain embodiments, the
A-value of R.sup.9 is at least 3 times greater than the A value of
R.sup.7.
[0151] In certain embodiments, the A-value of R.sup.7 is greater
than about 2.5 kcal/mol. In certain embodiments, the A-value of
R.sup.7 is greater than about 3 kcal/mol. In certain embodiments,
the A-value of R.sup.7 is greater than about 3.5 kcal/mol. In
certain embodiments, the A-value of R.sup.7 is greater than about 4
kcal/mol.
[0152] In certain embodiments, the A-value of R.sup.9 is greater
than about 2.5 kcal/mol. In certain embodiments, the A-value of
R.sup.9 is greater than about 3 kcal/mol. In certain embodiments,
the A-value of R.sup.9 is greater than about 3.5 kcal/mol. In
certain embodiments, the A-value of R.sup.9 is greater than about 4
kcal/mol.
[0153] In certain embodiments, the A-value of R.sup.9 is between
about 0 to about 2.5 kcal/mol. In certain embodiments, the A-value
of R.sup.9 is between about 0 to about 3 kcal/mol. In certain
embodiments, the A-value of R.sup.9 is between about 0 to about 3.5
kcal/mol. In certain embodiments, the A-value of R.sup.9 is between
about 0 to about 4 kcal/mol.
[0154] In certain embodiments, the A-value of R.sup.7 is between
about 0 to about 2.5 kcal/mol. In certain embodiments, the A-value
of R.sup.7 is between about 0 to about 3 kcal/mol. In certain
embodiments, the A-value of R.sup.7 is between about 0 to about 3.5
kcal/mol. In certain embodiments, the A-value of R.sup.7 is between
about 0 to about 4 kcal/mol.
[0155] In certain embodiments, the Southern Hemisphere of the metal
complex is of the formula (ii-e):
##STR00023##
[0156] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7, R.sup.8,
R.sup.9, and R.sup.10 are, as defined above and herein.
[0157] In certain embodiments of formula (ii-e), wherein R.sup.3,
R.sup.8 and R.sup.10 are hydrogen, the Southern Hemisphere of the
metal complex is of the formula (ii-f):
##STR00024##
[0158] wherein M, X, R.sup.7 and R.sup.9 are as defined above and
herein.
[0159] In certain embodiments, M is a metal selected from cobalt
and chromium. In certain embodiments, M is cobalt. In certain
embodiments, M is cobalt (III).
[0160] In certain embodiments, R.sup.7 is not
--C(CH.sub.3).sub.2Ph. In certain embodiments, R.sup.7 is not
--[C(CH.sub.3).sub.2CH.sub.2CH.sub.2N(Bu).sub.3].sup.+. In certain
embodiments, R.sup.7 is not --CH(CH.sub.2CH.sub.3)C.sub.6H.sub.5.
In certain embodiments, R.sup.7 is not
--C(CH.sub.3).sub.2CH.sub.2C(CH.sub.3).sub.3. In certain
embodiments, R.sup.7 is not --CH(C.sub.6H.sub.5)CHCH.sub.2. In
certain embodiments, R.sup.7 is not
--C(CH.sub.3).sub.2CH.sub.2CH.sub.3. In certain embodiments,
R.sup.7 is not 1-methyl-cyclohexyl. In certain embodiments, R.sup.7
is not cyclohexyl.
[0161] In certain embodiments, R.sup.9 is not
--C(CH.sub.3).sub.2C.sub.6H.sub.5. In certain embodiments, R.sup.9
is not --[C(CH.sub.3).sub.2CH.sub.2CH.sub.2N(Bu).sub.3].sup.+. In
certain embodiments, R.sup.9 is not
--C(CH.sub.3).sub.2CH.sub.2C(CH.sub.3).sub.3. In certain
embodiments, R.sup.9 is not --C(CH.sub.3).sub.3. In certain
embodiments, R.sup.9 is not --C(CH.sub.3).sub.2CH.sub.2CH.sub.3. In
certain embodiments, R.sup.9 is not --CH.sub.3. In certain
embodiments, R.sup.9 is not hydrogen.
[0162] In some embodiments, when R.sup.7 is --C(CH.sub.3).sub.2Ph,
R.sup.9 is other than --C(CH.sub.3).sub.2Ph. In some embodiments,
when R.sup.7 is
--[C(CH.sub.3).sub.2CH.sub.2CH.sub.2N(Bu).sub.3].sup.+, R.sup.9 is
other than --[C(CH.sub.3).sub.2CH.sub.2CH.sub.2N(Bu).sub.3].sup.+.
In some embodiments, when R.sup.7 is
--CH(CH.sub.2CH.sub.3)C.sub.6H.sub.5, R.sup.9 is other than
hydrogen. In some embodiments, when R.sup.7 is
--C(CH.sub.3).sub.2CH.sub.2C(CH.sub.3).sub.3, R.sup.9 is other than
--C(CH.sub.3).sub.2CH.sub.2C(CH.sub.3).sub.3. In some embodiments,
when R.sup.7 is --CH(C.sub.6H.sub.5)CHCH.sub.2, R.sup.9 is other
than --C(CH.sub.3).sub.3. In some embodiments, when R.sup.7 is
--C(CH.sub.3).sub.2CH.sub.2CH.sub.3, R.sup.9 is other than
--C(CH.sub.3).sub.3. In some embodiments, when R.sup.7 is
--C(CH.sub.3).sub.2CH.sub.2CH.sub.3, R.sup.9 is other than
--C(CH.sub.3).sub.2CH.sub.2CH.sub.3. In some embodiments, when
R.sup.7 is 1-methyl-cyclohexyl, R.sup.9 is other than
--C(CH.sub.3).sub.3. In some embodiments, when R.sup.7 is
1-methyl-cyclohexyl, R.sup.9 is other than
--C(CH.sub.3).sub.2CH.sub.2CH.sub.3. In some embodiments, when
R.sup.7 is cyclohexyl, R.sup.9 is other than --CH.sub.3.
[0163] In certain embodiments, the Southern Hemisphere is not
selected from:
##STR00025## ##STR00026##
[0164] wherein X is as defined above and herein.
[0165] Any of the above formulae (i-a) to (i-q) may be combined
with any of the above formulae (ii-a) to (ii-f) to provide novel
metal complexes.
[0166] For example, in certain embodiments, the present disclosure
provides a metal complex of the formula (I-a):
##STR00027##
[0167] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A, R.sup.4B,
R.sup.5A, R.sup.5B, R.sup.6A, and R.sup.6B are as defined above and
herein.
[0168] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-b):
##STR00028##
[0169] wherein M, X, R.sup.1, R.sup.2 and R.sup.3 are as defined
above and herein.
[0170] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-c):
##STR00029##
[0171] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.5A, R.sup.5B,
R.sup.12 and c are as defined above and herein.
[0172] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-d):
##STR00030##
[0173] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A, R.sup.4B,
R.sup.5A, and R.sup.5B are as defined above and herein.
[0174] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-e):
##STR00031##
[0175] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A, R.sup.5A,
R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B,
R.sup.16A, R.sup.16B are as defined above and herein.
[0176] In certain embodiments, the present disclosure provides a
metal complex of any one of the formulae (I-f) to (I-i):
##STR00032##
[0177] or any mixture thereof;
[0178] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A, R.sup.5A,
R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B,
R.sup.16A, R.sup.16B are as defined above and herein.
[0179] Where a particular enantiomer is preferred, it may, in some
embodiments be provided substantially free of the corresponding
enantiomer, and may also be referred to as "optically enriched."
"Optically-enriched," as used herein, means that the compound is
made up of a significantly greater proportion of one enantiomer. In
certain embodiments the compound is made up of at least about 90%
by weight of a preferred enantiomer. In other embodiments the
compound is made up of at least about 95%, 98%, or 99% by weight of
a preferred enantiomer.
[0180] Thus, in certain embodiments, the present disclosure
provides an optically enriched metal complex of any one of the
formulae (I-f) to (I-i). In certain embodiments, the present
disclosure provides an optically enriched metal complex of formula
(I-f). In certain embodiments, the present disclosure provides an
optically enriched metal complex of formula (I-g). In certain
embodiments, the present disclosure provides an optically enriched
metal complex of formula (I-h). In certain embodiments, the present
disclosure provides an optically enriched metal complex of formula
(I-i).
[0181] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-j):
##STR00033##
[0182] wherein M, X, R.sup.1, R.sup.2 and R.sup.3 are as defined
above and herein.
[0183] In certain embodiments, the present disclosure provides a
metal complex of any one of the formulae (I-k) to (I-n):
##STR00034##
[0184] or any mixture thereof;
[0185] wherein M, X, R.sup.1, R.sup.2 and R.sup.3 are as defined
above and herein.
[0186] In certain embodiments, the present disclosure provides an
optically enriched metal complex of any one of the formulae (I-k)
to (I-n). In certain embodiments, the present disclosure provides
an optically enriched metal complex of formula (I-k). In certain
embodiments, the present disclosure provides an optically enriched
metal complex of formula (I-l). In certain embodiments, the present
disclosure provides an optically enriched metal complex of formula
(I-m). In certain embodiments, the present disclosure provides an
optically enriched metal complex of formula (I-n).
[0187] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-o):
##STR00035##
[0188] wherein d, M, X, R.sup.1, R.sup.2, R.sup.3 and R.sup.17 are
as defined above and herein.
[0189] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-p):
##STR00036##
[0190] wherein d, M, X, R.sup.1, R.sup.2 and R.sup.3 are as defined
above and herein.
[0191] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-q):
##STR00037##
[0192] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.11, R.sup.4A,
R.sup.5A, R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A,
R.sup.15B, R.sup.16A, R.sup.16B are as defined above and
herein.
[0193] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-r):
##STR00038##
[0194] wherein b, R.sup.11, M and X are as defined above and
herein.
[0195] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-s):
##STR00039##
[0196] wherein b, d, M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.11 and
R.sup.17 are as defined above and herein.
[0197] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-t):
##STR00040##
[0198] wherein b, M, X, R.sup.1, R.sup.2, R.sup.3 and R.sup.11 are
as defined above and herein.
[0199] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-u):
##STR00041##
[0200] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A, R.sup.5A,
R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.13A, R.sup.13B,
R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B, R.sup.16A, R.sup.16B
are as defined above and herein.
[0201] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-v):
##STR00042##
[0202] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7, R.sup.8,
R.sup.9 and R.sup.10 are as defined above and herein.
[0203] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-w):
##STR00043##
[0204] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A, R.sup.5A,
R.sup.7, R.sup.9, R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B,
R.sup.15A, R.sup.15B, R.sup.16A, R.sup.16B are as defined above and
herein.
[0205] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-x):
##STR00044##
[0206] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7 and R.sup.9
are as defined above and herein.
[0207] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-y):
##STR00045##
[0208] wherein M, X, R.sup.4A, R.sup.5A, R.sup.7, R.sup.8, R.sup.9,
R.sup.10, R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A,
R.sup.15B, R.sup.16A, R.sup.16B are as defined above and
herein.
[0209] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-z):
##STR00046##
[0210] wherein M, X, R.sup.4A, R.sup.5A, R.sup.7, R.sup.9,
R.sup.13A, R.sup.13B, R.sup.14A, R.sup.14B, R.sup.15A, R.sup.15B,
R.sup.16A, R.sup.16B are as defined above and herein.
[0211] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-aa):
##STR00047##
[0212] wherein M, X, R.sup.7 and R.sup.9 are as defined above and
herein.
[0213] In certain embodiments, the present disclosure provides a
metal complex of the formulae (I-bb) to (I-ee):
##STR00048##
[0214] or any mixture thereof.
[0215] In certain embodiments, the present disclosure provides an
optically enriched metal complex of any one of the formulae (I-bb)
to (I-ee). In certain embodiments, the present disclosure provides
an optically enriched metal complex of formula (I-bb). In certain
embodiments, the present disclosure provides an optically enriched
metal complex of formula (I-cc). In certain embodiments, the
present disclosure provides an optically enriched metal complex of
formula (I-dd). In certain embodiments, the present disclosure
provides an optically enriched metal complex of formula (I-ee).
[0216] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-ff):
##STR00049##
[0217] wherein d, M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4A,
R.sup.5A, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.17 are as
defined above and herein.
[0218] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-gg):
##STR00050##
[0219] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7, R.sup.8,
R.sup.9 and R.sup.10 are as defined above and herein.
[0220] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-hh):
##STR00051##
[0221] wherein d, M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7, R.sup.9
and R.sup.17 are as defined above and herein.
[0222] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-ii):
##STR00052##
[0223] wherein M, X, R.sup.1, R.sup.2, R.sup.3, R.sup.7 and R.sup.9
are as defined above and herein.
[0224] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-jj):
##STR00053##
[0225] wherein d, M, X, R.sup.4A, R.sup.5A, R.sup.7, R.sup.8,
R.sup.9, R.sup.10 and R.sup.17 are as defined above and herein.
[0226] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-kk):
##STR00054##
[0227] wherein d, M, X, R.sup.7, R.sup.9 and R.sup.17 are as
defined above and herein.
[0228] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-ll):
##STR00055##
[0229] wherein M, X, R.sup.7 and R.sup.9 are as defined above and
herein.
[0230] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-mm):
##STR00056##
[0231] wherein M, X, Ring A, R.sup.3, R.sup.7 and R.sup.9 are as
defined above and herein.
[0232] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-nn):
##STR00057##
[0233] wherein M, X, Ring A, R.sup.1, R.sup.2, R.sup.3, R.sup.7 and
R.sup.9 are as defined above and herein.
[0234] In certain embodiments, the present disclosure provides a
metal complex of the formula (I-oo):
##STR00058##
[0235] wherein M, X, R.sup.7, R.sup.9, R.sup.4A, R.sup.4B,
R.sup.5A, R.sup.5B, and R.sup.6A, R.sup.6B are as defined above and
herein.
III. Exemplary Metal Complexes
[0236] In certain embodiments, the metal complex is selected from
any one of the following, wherein X is absent or is a nucleophilic
ligand:
##STR00059## ##STR00060## ##STR00061##
[0237] In certain embodiments, the metal complex is selected from
any one of the following, wherein X is absent or is a nucleophilic
ligand:
##STR00062## ##STR00063## ##STR00064##
[0238] In certain embodiments, the metal complex has the following
structure, wherein X is absent or is a nucleophilic ligand:
##STR00065##
[0239] In certain embodiments, the metal complex has the following
structure, wherein X is absent or is a nucleophilic ligand:
##STR00066##
[0240] In certain embodiments, the metal complex has the following
structure, wherein X is absent or is a nucleophilic ligand:
##STR00067##
[0241] In certain embodiments, the metal complex has the following
structure, wherein X is absent or is a nucleophilic ligand:
##STR00068##
[0242] In certain embodiments, the metal complex has the following
structure, wherein X is absent or is a nucleophilic ligand:
##STR00069##
[0243] In certain embodiments, X is absent.
[0244] In certain embodiments, X is --O(C.dbd.O)C.sub.6F.sub.5
(i.e., --OBzF.sub.5). In certain embodiments, X is
--OC(.dbd.O)CH.sub.3. In certain embodiments, X is
--OC(.dbd.O)CF.sub.3. In certain embodiments, X is --NC. In certain
embodiments, X is --Cl. In certain embodiments, X is --Br. In
certain embodiments, X is N.sub.3.
[0245] In certain embodiments, the metal complex is a cobalt (Co)
complex selected from any of the following structures:
##STR00070## ##STR00071## ##STR00072##
[0246] In certain embodiments, the metal complex is a cobalt (Co)
complex selected from any of the following structures:
##STR00073## ##STR00074## ##STR00075##
[0247] In certain embodiments, the metal complex is a cobalt (Co)
complex having the following structure:
##STR00076##
[0248] In certain embodiments, the metal complex is a cobalt (Co)
complex having the following structure:
##STR00077##
[0249] In certain embodiments, the metal complex is a cobalt (Co)
complex having the following structure:
##STR00078##
[0250] In certain embodiments, the metal complex is a cobalt (Co)
complex having the following structure:
##STR00079##
[0251] In certain embodiments, the metal complex is a cobalt (Co)
complex having the following structure:
##STR00080##
IV. Methods of Making Poly(Ethylene Carbonate) Polymers
[0252] The present disclosure also provides methods of making
various poly(ethylene carbonate) polymers. As used herein,
poly(ethylene carbonate) polymers are provided via polymerization
of ethylene oxide (EO) and carbon dioxide (CO.sub.2) in the
presence of a metal complex, and encompass encompasses
poly(ethylene carbonate) (PEC), as well as polymers which comprise
poly(ethylene carbonate), such as, for example, polyethylene
oxide-co-polyethylene carbonate.
[0253] For example, in one aspect, the present disclosure provide a
method of synthesizing a poly(ethylene carbonate) polymer, wherein
the polymer is made up of Y, and optionally Z, and wherein the
percentage of Y is greater than the percentage of Z,
##STR00081##
[0254] the method comprising reacting ethylene oxide and carbon
dioxide in the presence of a metal complex.
[0255] In certain embodiments, the polymer has greater than about
85 percent of Y. In certain embodiments, the polymer has greater
than about 90% of Y. In certain embodiments, the polymer has
greater than about 95% of Y. In certain embodiments, the polymer
has greater than about 99% of Y. In certain embodiments, the
polymer is substantially all Y and is substantially free of Z.
[0256] In certain embodiments, the polymer is an alternating
polymer of ethylene oxide and carbon dioxide (e.g., with regular
alternating units of ethylene oxide and carbon dioxide).
[0257] For example, wherein the polymer is substantially all Y and
is substantially free of Z, the polymer an alternating polymer of
the formula:
##STR00082##
[0258] wherein P is an integer of between about 10 and about
15,000, inclusive, and
[0259] each F and G are, independently, a suitable terminating
group.
[0260] In certain embodiments, F is hydrogen. In certain
embodiments F is a hydroxyl-protecting group. In certain
embodiments F is an acyl group. In certain embodiments F is a silyl
group. In certain embodiments, G is X, where X is as described
above. In certain embodiments, G is a hydroxyl group.
[0261] In certain embodiments, P is an integer of between about
10,000 to about 15,000, inclusive. In certain embodiments, P is an
integer of between about 12,000 to about 15,000, inclusive.
[0262] In certain embodiments, the metal complex is a zinc, cobalt,
chromium, aluminum, titanium, ruthenium or manganese complex. In
certain embodiments, the metal complex is an aluminum complex. In
certain embodiments, the metal complex is a chromium complex. In
certain embodiments, the complex metal is zinc complex. In certain
embodiments, the metal complex is a titanium complex. In certain
embodiments, the metal complex is a ruthenium complex. In certain
embodiments, the metal complex is a manganese complex. In certain
embodiments, the metal complex is cobalt complex. In certain
embodiments, wherein the metal complex is a cobalt complex, the
cobalt metal has a valency of +3 (i.e., Co(III)).
[0263] In certain embodiments, the metal complex is any of the
above described metal complexes of the formula (I), or subsets
thereof.
[0264] In another aspect, the present disclosure provides a method
of synthesizing a poly(ethylene carbonate) polymer, the method
comprising the step of reacting ethylene oxide with carbon dioxide
in the presence of a cobalt complex of any of the above described
metal complexes of the formula (I), or a subset thereof, wherein M
is cobalt.
Reaction Conditions
[0265] In certain embodiments, any of the above methods further
comprise a co-catalyst.
[0266] In certain embodiments, the co-catalyst is a Lewis base.
Exemplary Lewis bases include, but are not limited to:
N-methylimidazole (N-MeIm), dimethylaminopyridine (DMAP),
1,4-diazabicyclo[2.2.2]octane (DABCO), triethyl amine, and
diisopropyl ethyl amine.
[0267] In certain embodiments, the co-catalyst is a salt. In
certain embodiments, the co-catalyst is an ammonium salt, a
phosphonium salt or an arsonium salt. In certain embodiments, the
co-catalyst is an ammonium salt. Exemplary ammonium salts include,
but are not limited to: (n-Bu).sub.4NCl, (n-Bu).sub.4NBr,
(n-Bu).sub.4NN.sub.3, [PPN]Cl, [PPN]Br, and [PPN]N.sub.3,
Ph.sub.3PCPh.sub.3]Cl [PPN]O(C.dbd.O)R.sup.c
(PPN=Bis(triphenylphosphoranylidene) ammonium)). In certain
embodiments, the co-catalyst is a phosphonium salt. In certain
embodiments, the co-catalyst is an arsonium salt.
[0268] In certain embodiments, the co-catalyst is the ammonium salt
bis(triphenylphosphoranylidene)ammonium chloride ([PPN]Cl).
[0269] In certain embodiments, the anion of the salt co-catalyst
has the same structure as the ligand X of the above described metal
complexes of the formula (I), or subsets thereof, wherein X is a
nucleophilic ligand. For example, in certain embodiments, the
co-catalyst is ([PPN]X) or (n-Bu).sub.4NX.
[0270] In certain embodiments, any of the above methods comprise a
ratio of about 500:1 to about 500,000:1 of ethylene oxide to metal
complex. In certain embodiments, any of the above methods comprise
a ratio of about 500:1 to about 100,000:1 of ethylene oxide to
metal complex. In certain embodiments, any of the above methods
comprise a ratio of about 500:1 to about 50,000:1 of ethylene oxide
to metal complex. In certain embodiments, any of the above methods
comprise a ratio of about 500:1 to about 5,000:1 of ethylene oxide
to metal complex. In certain embodiments, any of the above methods
comprise a ratio of about 500:1 to about 1,000:1 of ethylene oxide
to metal complex.
[0271] In certain embodiments, any of the above methods comprise
ethylene oxide present in amounts between about 0.5 M to about 20
M. In certain embodiments, ethylene oxide is present in amounts
between about 0.5 M to about 2 M. In certain embodiments, ethylene
oxide is present in amounts between about 2 M to about 5 M. In
certain embodiments, ethylene oxide is present in amounts between
about 5 M to about 20 M. In certain embodiments, ethylene oxide is
present in an amount of about 20 M. In certain embodiments, liquid
ethylene oxide comprises the reaction solvent.
[0272] In certain embodiments, CO.sub.2 is present at a pressure of
between about 30 psi to about 800 psi. In certain embodiments,
CO.sub.2 is present at a pressure of between about 30 psi to about
500 psi. In certain embodiments, CO.sub.2 is present at a pressure
of between about 30 psi to about 400 psi. In certain embodiments,
CO.sub.2 is present at a pressure of between about 30 psi to about
300 psi. In certain embodiments, CO.sub.2 is present at a pressure
of between about 30 psi to about 200 psi. In certain embodiments,
CO.sub.2 is present at a pressure of between about 30 psi to about
100 psi. In certain embodiments, CO.sub.2 is present at a pressure
of between about 30 psi to about 80 psi. In certain embodiments,
CO.sub.2 is present at a pressure of about 30 psi. In certain
embodiments, CO.sub.2 is present at a pressure of about 50 psi. In
certain embodiments, CO.sub.2 is present at a pressure of about 100
psi. In certain embodiments, the CO.sub.2 is supercritical.
[0273] In certain embodiments, any of the above methods comprise
the reaction to be conducted at a temperature of between about
0.degree. C. to about 100.degree. C. In certain embodiments, the
reaction is conducted at a temperature of between about 23.degree.
C. to about 100.degree. C. In certain embodiments, the reaction to
be conducted at a temperature of between about 23.degree. C. to
about 80.degree. C. In certain embodiments, the reaction to be
conducted at a temperature of between about 23.degree. C. to about
50.degree. C. In certain embodiments, the reaction to be conducted
at a temperature of about 23.degree. C.
[0274] In certain embodiments, the reaction step of any of the
above methods does not further comprise a solvent.
[0275] However, in certain embodiments, the reaction step of any of
the above methods does further comprise one or more solvents. In
certain embodiments, the solvent is an organic solvent. In certain
embodiments, the solvent is an organic ether. In certain
embodiments, the solvent is an aromatic hydrocarbon. In certain
embodiments the solvent is a ketone.
[0276] In certain embodiments suitable solvents include, but are
not limited to: Methylene Chloride, Chloroform, 1,2-Dichloroethane,
Propylene Carbonate, Acetonitrile, Dimethylformamide,
N-Methyl-2-pyrrolidone, Dimethyl Sulfoxide, Nitromethane,
Caprolactone, 1,4-Dioxane, and 1,3-Dioxane.
[0277] In certain other embodiments, suitable solvents include, but
are not limited to: Methyl Acetate, Ethyl Acetate, Acetone, Methyl
Ethyl Ketone, Propylene Oxide, Tretrahydrofuran, Monoglyme
Triglyme, Propionitrile, 1-Nitropropane, Cyclohexanone.
[0278] In certain embodiments, the reaction step of any of the
above methods produces ethylene carbonate (EC) as a by-product in
amounts of less than about 20%. In certain embodiments, ethylene
carbonate (EC) is produced as a by-product in amounts of less than
about 15%. In certain embodiments, ethylene carbonate (EC) is
produced as a by-product in amounts of less than about 10%. In
certain embodiments, ethylene carbonate (EC) is produced as a
by-product in amounts of less than about 5%. In certain
embodiments, ethylene carbonate (EC) is produced as a by-product in
amounts of less than about 1%. In certain embodiments, the reaction
does not produce any detectable by-products (e.g., as detectable by
.sup.1H-NMR and/or liquid chromatography (LC)).
Tapered and Block Co-Polymers
[0279] As is understood from the above, the poly(ethylene
carbonate) polymer is a co-polymer of units "Y" and "Z":
##STR00083##
[0280] In certain embodiments, the poly(ethylene carbonate) polymer
is a tapered co-polymer of units Y and Z (e.g., wherein the
incorporation of Z increases or decreases along the length of a
given polymer chain.):
[0281] In certain embodiments, the poly(ethylene carbonate) polymer
is a block co-polymer of homopolymer units of Y and Z; the union of
the homopolymer subunits may require an intermediate non-repeating
subunit, known as a junction block. Block copolymers with two or
three distinct blocks are called diblock copolymers and triblock
copolymers, respectively.
[0282] In certain embodiments, the tapered or block co-polymer of
poly(ethylene carbonate) is of the formula:
##STR00084##
[0283] wherein each instance of P and Q are, independently, an
integer of between about 10 to about 10,000, inclusive, and wherein
R is an integer ranging from about 1 to about 20,
[0284] each F and G are, independently, suitable terminating
groups, as described above and herein.
[0285] For example, in certain embodiments, the present disclosure
provides a method of making a poly(ethylene carbonate) block
co-polymer, comprising the steps of (i) providing a polyethylene
oxide (PEO) polymer, and (ii) reacting the polyethylene oxide
polymer with ethylene oxide and carbon dioxide in the presence of a
metal complex. In certain embodiments, the metal complex is a metal
complex of formula (I), or any subset thereof.
[0286] In certain embodiments, the polyethylene oxide polymer of
step (i) is provided by reacting ethylene oxide in the presence of
a metal complex. In certain embodiments, the metal complex is a
metal complex of formula (I), or any subset thereof.
[0287] In certain embodiments block copolymer compositions may be
produced by varying or removing the CO.sub.2 pressure during part
of the polymerization process. When the CO2 pressure is low or
non-existent, the catalyst will produce polymer having a higher
degree of ether linkages than when the CO2 pressure is high. Thus,
in certain embodiments of the present disclosure the polymerization
may be initiated with any of the metal complexes described above at
a relatively high CO.sub.2 pressure (for example, higher than 100
psi, higher than about 200 psi, or higher than about 400 psi).
These conditions will produce polymer having a predominance of
carbonate linkages. After a length of time, the CO.sub.2 pressure
is lowered (for example to less than 100 psi, less than 50 psi, or
to atmospheric pressure) or is removed completely. These conditions
result in new block with more ether bonds being incorporated into
the growing polymer chains. The above described process can
optionally be repeated one or more times to build diblock, triblock
or multiblock polymers. Additionally, several different CO.sub.2
pressure levels can be used in the process to produce polymers with
several different block types. In certain embodiments, the CO.sub.2
pressure is initially low and is then increased. In certain other
embodiments the CO.sub.2 pressure is varied periodically. In
certain other embodiments, the CO.sub.2 pressure is varied smoothly
over time to form tapered polyether co polycarbonate polymer
compositions or blocks with a tapered copolymeric structure.
EXEMPLIFICATION
Example 1
Highly Active Cobalt Catalysts for Alternating Copolymerization of
Ethylene Oxide and Carbon Dioxide
[0288] The inventors have recently found that (salcy)CoOBzF.sub.5
(salcy=N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane;
OBzF.sub.5=pentafluorobenzoate; 1) efficiently copolymerizes
cyclohexene oxide (CHO) or propylene oxide (PO) with CO.sub.2.
However, there has been no report using 1 for the copolymerization
of EO and CO.sub.2 to make PEC. Herein is reported the development
of highly active Co(salcy) catalysts for the copolymerization of
EO/CO.sub.2 under low CO.sub.2 pressure to produce copolymers with
high carbonate percentages.
[0289] The recent success using 1 with
bis(triphenylphosphoranylidene)ammonium chloride ([PPN]Cl) to
copolymerize PO and CO.sub.2 led us to investigate this catalytic
system for the copolymerization of EO and CO.sub.2 (Scheme 1 and
Table 2) (see (a) Moore, D. R.; Cheng, M.; Lobkovsky, E. B.;
Coates, G. W. Angew. Chem. Int. Ed. 2002, 41, 2599-2602. (b) Cheng,
M.; Moore, D. R.; Reczek, J. J.; Chamberian, B. M.; Lobkovsky, E.
B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 8738-8749. (c)
Cheng, M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 1998,
120, 11018-11019. (d) Allen, S. D.; Moore, D. R.; Lobkovsky, E. B.;
Coates, G. W. J. Am. Chem. Soc. 2002, 124, 14284-14285. (e) Qin, Z.
Q.; Thomas, C. M.; Lee, S.; Coates, G. W. Angew. Chem. Int. Ed.
2003, 42, 5484-5487. (f) Cohen, C. T.; Chu, T.; Coates, G. W. J.
Am. Chem. Soc. 2005, 127, 10869-10878. (g) Cohen, C. T.; Coates, G.
W. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 5182-5191).
##STR00085##
TABLE-US-00002 TABLE 2 Co Catalyst R.sup.7 R.sup.9 1 t-Bu t-Bu 2
--C(Me)(Et).sub.2 t-Bu 3 --C(Et).sub.3 t-Bu 4
--C(Me).sub.2CH.sub.2C(Me).sub.3 t-Bu 5 --C(Et).sub.3 --CH.sub.3 6
--C(Et).sub.3 i--Pr 7 --CH.sub.3 --C(Et).sub.3 8 t-Amyl
(--CH.sub.2C(CH.sub.3) t-Amyl (--CH.sub.2C(CH.sub.3) 9 Cumyl
(--C(CH.sub.3).sub.2Ph) Cumyl (--C(CH.sub.3).sub.2Ph) --OBzF.sub.5O
= --O(C.dbd.O)C.sub.6F.sub.5
Co Catalysts
##STR00086## ##STR00087##
[0291] Reacting 1/[PPN]Cl with EO under 100 psi CO.sub.2 at
22.degree. C. produced a very viscous solution after just 1 hour,
which suggested that 1/[PPN]Cl was active for EO/CO.sub.2
copolymerization. Further analysis of the product revealed
poly(EO-co-EC) had been synthesized (entry 1, Table 3).
[0292] The .sup.1H NMR spectrum of the polymer produced by
1/[PPN]Cl is shown in FIG. 1A. In addition to the expected
polycarbonate peak (a), shifts were also observed which correspond
to ether linkages (b, c, d), indicating that the copolymerization
under these conditions is not perfectly alternating. Ether
incorporation is problematic because it negatively affects the gas
barrier properties. Despite many changes in the reaction
conditions, we were unable to completely suppress ether
incorporation using catalyst 1.
TABLE-US-00003 TABLE 3 Experimental Conditions and Results of
Copolymerization of EO and CO.sub.2.sup.a carbon- cata- [Co]
yield.sup.b TOF.sup.c ate.sup.d PEC: EC.sup.e M.sub.n.sup.f
M.sub.w/ entry lyst (mM) (%) (h.sup.-1) (%) (% PEC) (g/mol)
M.sub.n.sup.f 1 1 10 47 940 67 83 25,900 1.6 2.sup.g 1 10 21 830 85
99 14,100 1.4 3 1 5.0 21 830 89 97 36,700 1.4 4.sup.h 1 2.0 16 520
93 >99 34,800 1.5 5.sup.i 1 5.0 19 760 90 99 24,400 1.3 6.sup.j
1 5.0 13 510 89 99 15,700 1.3 7.sup.k 1 10 26 170 84 >99 22,800
1.2 8.sup.l 1 5.0 46 610 76 99 29,800 1.5 9 2 10 41 820 99 93
28,900 1.3 10 3 10 27 540 >99 95 32,400 1.3 11 4 10 20 400
>99 95 27,100 1.4 12 5 10 13 250 >99 68 28,100 1.4 13 6 10 26
530 >99 86 26,500 1.3 14 7 10 34 680 98 91 26,100 1.4 15 8 10 45
910 97 94 33,700 1.4 16 9 10 22 430 >99 80 26,000 1.4 17 10 10
27 540 92 81 29,400 1.5 .sup.aPolymerizations run in neat ethylene
oxide (EO); [EO].sub.0 = 20M; [Co].sub.0 = [[PPN]Cl].sub.0; with
100 psi of CO.sub.2 at 22.degree. C. for 1 h. .sup.bDetermined by
crude products mass assuming that both PEC and EC are present.
.sup.cTurnover frequency = mol PEC/mol Co h. .sup.dDetermined by
.sup.1H NMR spectroscopy of the purified copolymer.
.sup.eDetermined by .sup.1H NMR spectroscopy of PEC and EC of the
crude product. .sup.fDetermined by gel permeation chromatography
calibrated with PMMA standards in DMF. .sup.g30 min. .sup.h3 h.
.sup.iP.sub.CO.sub.2 = 80 psi. .sup.jP.sub.CO.sub.2 = 50 psi.
.sup.k0.degree. C. for 3 h. .sup.l[EO].sub.0 = 10M in 1,4-dioxane
for 1.5 h.
[0293] In order to achieve a perfectly alternating
copolymerization, the catalyst structure was optimized by varying
ligand substituents. Several catalysts were prepared by changing
R.sup.7 and/or R.sup.9 (Scheme 1), and screened for EO/CO.sub.2
copolymerization (Table 3). Catalysts 1-10 were active for the
copolymerization and their activities were influenced by the
substituents R.sup.7 and R.sup.9. With tert-butyl groups at R.sup.7
and R.sup.9 (1), the copolymerization proceeded rapidly to give 47%
EO conversion in 1 hour with a high turnover frequency (TOF) (entry
1). After 1 hour, the copolymerization solution was very viscous,
preventing the dissolution of CO.sub.2 and effectively stopping the
polymerization. In addition, back biting occurred to produce 17%
ethylene carbonate (EC) (entry 1). Reducing the reaction time to 30
min kept viscosity low, thus reduced back biting and increased
carbonate percentage (entry 2). Compared with 1, 2 bearing bulkier
substituents at R.sup.1 gave a copolymer with higher carbonate
percentage, although the catalytic activity slightly decreased
(entry 9). This suggested the bulkiness of the R.sup.7 substituent
significantly impacts carbonate percentage. Complexes 3 and 4
produced nearly perfect alternating PEC (entry 10 and 11). The
carbonate content followed the trend 1<2<3<4 and the
activity trend was 1>2>3>4. This demonstrates that
carbonate percentage increases with steric bulk while activity
decreases.
[0294] The effects of changing R.sup.9 were also examined. Catalyst
5, bearing a Me group, afforded the slowest polymerization
resulting a TOF of 250 h.sup.-1, however, the resulting copolymer
exhibited very high carbonate percentage, 99.1% (entry 12). Complex
6 where R.sup.9=i-Pr showed similar catalytic activity and similar
carbonate percentage as complex 3 (entry 13). This observation
suggests that the substituent R.sup.9 does not significantly
influence the carbonate percentage but does influence the rate.
[0295] Complex 7, which has a small substituent at R.sup.7 and a
bulky substituent at R.sup.9, was expected to show high activity
and low carbonate percentage in the resulting copolymer. The
catalytic activity was relatively high, however, to our surprise,
98% carbonate percentage was obtained regardless of the small
substituent at R.sup.7. This result suggests that the larger
substituents for R.sup.7 and R.sup.9 improve the activity and the
carbonate percentage.
[0296] Complexes 8 and 9 were rapidly prepared from commercially
available disubstituted phenols and were also evaluated for the
copolymerization. Catalyst 8 exhibited a high TOF of 910 h.sup.-1
comparable to 1 and gave higher carbonate percentage of 96.8%
(entry 15). Catalyst 9 gave a TOF of 430 n.sup.-1, which is slower
than 1 and 8. However, 9 gave very high carbonate percentage of
99.1% (entry 16). Among these three catalysts, the least sterically
hindered compound 1, gave the highest activity and the lowest
carbonate percentage, while the most sterically hindered compound
9, gave the lowest activity but the highest carbonate percentage.
This mirrors the trend observed with compounds 1-4.
[0297] We also screened 10, which is identical to 1, but has a
phenyl backbone in place of the cyclohexyl. A similar version of
this catalyst, with an acetate initiator, induces the
stereoselective homopolymerization of PO to give perfectly
isotactic polypropylene oxide). The catalytic activity and the
carbonate linkage content were 540 h.sup.-1 and 92.1%,
respectively, not as high active as with 1, although the structure
is very similar to that of 1 (entry 17).
[0298] Reducing the concentration of 1 caused a decrease in the
catalytic activity but an increase of the carbonate linkage (entry
3 and 4). This result suggests that the insertion rates of EO to
alkoxide and carbonate termini in the copolymer depend on the Co
concentration, and the EO insertion may involve a bimetallic
mechanism of the catalyst.
[0299] Copolymerizations were also performed by filling CO.sub.2
into the solution of EO, Co catalyst, and cocatalyst (PPNCl) under
30-400 psi at room temperature to give poly(ethylene carbonate)
(PEC). The catalystic activities were higher than those of other
catalyst to give ca. 100 g-polymer/g-catalysth (for catalyst 1).
The catalytic activities were compared among the catalysts 2, 8, 9
(Table 4). It proved that the more bulky substituent in the
catalyst, the less active.
TABLE-US-00004 TABLE 4 Comparison of Co catalyst.sup.a) Activity,
g-polymer/g- Carbonate Catalyst Yield, % TOF, h.sup.-1 cat h
Linkage, % 1 44.3 886 95.7 66.0 8 42.2 844 85.3 96.7 9 21.5 430
35.7 99.1 2 38.1 762 77.0 98.9 .sup.a)EO = 100 mmol, Co cat = 0.050
mmol, PPNCl = 0.050 mmol, P.sub.CO2 = 100 psi, Polymerization time
= 1 h.
[0300] The effect of the catalyst concentration (of catalyst 1) to
the catalytic activity was also investigated. As shown in Table 5,
the catalytic activity increased with the catalyst 1
concentration.
TABLE-US-00005 TABLE 5 Effect of Catalyst Concentration.sup.a)
Activity, [Co 1].sub.0, Reaction Yield, g-polymer/ Carbonate mM
Time, h % TOF, h.sup.-1 g-cat h Linkage, % 1.0 2 3.1 310 32.6 93.2
5.0 2.5 37.7 602 64.4 85.2 9.1 1 31.9 708 74.8 71.6 10 1 44.3 886
95.7 66.0 .sup.a)[EO].sub.0 = 20 M (bulk), [Co].sub.0 =
[PPNCl].sub.0, P.sub.CO2 = 100 psi.
[0301] Table 5 shows the effect of CO.sub.2 pressure to catalytic
activity of catalyst 1. The activity increased with the pressure at
low pressure. However, it had a maximum about 200 psi.
TABLE-US-00006 TABLE 6 Effect of CO.sub.2 Pressure.sup.a) Activity,
Reaction g-polymer/ Carbonate P.sub.CO2 Time, h Yield, % TOF,
h.sup.-1 g-cat h Linkage, % 50 4 4.1 203 19.9 96.0 100 2 3.1 310
32.6 93.2 200 3 9.1 606 62.9 74.4 400 2 2.8 278 29.2 64.9
.sup.a)[EO].sub.0 = 20 M (bulk), [Co 1].sub.0 = [PPNCl].sub.0 = 1.0
mM.
[0302] From .sup.1H NMR analysis, the obtained polymers mainly
consist of carbonate linkage but have some amount of ether linkage,
which depended on the reaction conditions (catalyst concentration,
CO.sub.2 pressure, and reaction temperature) and substituents of
the catalyst (see FIGS. 1 and 2). The most active catalyst 1 had
the least carbonate linkage and the least active catalyst 2 had the
highest carbonate linkage. Especially, the catalyst 2 produced
almost perfect PEC. The effect of the catalyst concentration to the
carbonate linkage were also shown in Table 5. It showed that the
carbonate linkage increased by decreasing the catalyst
concentration. The CO.sub.2 pressure also affected the carbonate
linkage. Opposite to expected, the carbonate linkage decreased by
increasing the pressure as shown in Table 6.
[0303] Catalyst 15 has also been found to be effective to provide a
poly(ethylene carbonate-co-ethylene oxide) polymer.
##STR00088##
EO:CO:PPNCl=2000:1:1; PCO.sub.2=100 psi; 3 hr; 14% yield of
polymer; TOF=92 h.sup.-1; carbonate linkage 96%; PEC:EC=93:7.
[0304] In conclusion, we have reported the first examples of
Co-catalyzed EO/CO.sub.2 copolymerization. The polymerizations were
very fast even under relatively low pressure. The obtained
copolymer consists not only of carbonate linkages but also ether
linkages which indicates both EO/CO.sub.2 alternating
copolymerization and EO homopolymerization are occurring during the
copolymerization. The ether content can be decreased through the
catalyst design. Catalyst 3 gave a high catalytic activity and a
copolymer with the greatest carbonate content, which is almost a
perfectly alternating copolymer.
Example 2
Polymerization of Ethylene Oxide (PEO)
[0305] (Salcy)CoOBzF.sub.5 induced ethylene oxide (EO)
polymerization in the presence of PPNCl. The activity was strongly
depended on the PPNCl/Co ratio (see Table 7 and FIG. 3).
##STR00089##
TABLE-US-00007 TABLE 7 Effect of [PPNCl]/[Co] Product [PPNCl]/[Co]
Mass, g Yield, % TOF, h.sup.-1 0.2 0.1535 3.5 836 0.3 0.3252 7.4
1777 0.5 0.2065 4.7 1125 0.7 0.1917 4.4 1044 1 0.1030 2.3 561
[EO].sub.0 = 20 M, [Co].sub.0 = 5.0 mM, [PPNCl].sub.0 = 1.0-5.0 mM,
rt 10 min.
Example 3
Synthesis of Block Copolymer of PEO-b-PEC
[0306] The one-pot PEO-b-PEC synthesis was then examined. PEO was
polymerized in a glass autoclave first, and then the reaction
solution was pressurized with CO.sub.2 to undergo EO/CO.sub.2
copolymerization. This polymer consists of hard segment (PEO)/soft
segment (PEC), and is thus considered to have a new function (see
FIGS. 4A-4B depicting the TGA and DSC analyses of PEO-b-PEC).
##STR00090##
Other Embodiments
[0307] The foregoing has been a description of certain non-limiting
preferred embodiments. Those of ordinary skill in the art will
appreciate that various changes and modifications to this
description may be made without departing from the spirit or scope
of the present disclosure, as defined in the following claims.
* * * * *