U.S. patent application number 12/115139 was filed with the patent office on 2008-08-28 for alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis.
This patent application is currently assigned to Evonik Degussa GmbH. Invention is credited to Wolfgang Anton Herrmann, Wolfgang Schattenmann, Thomas Weskamp.
Application Number | 20080207911 12/115139 |
Document ID | / |
Family ID | 7863687 |
Filed Date | 2008-08-28 |
United States Patent
Application |
20080207911 |
Kind Code |
A1 |
Herrmann; Wolfgang Anton ;
et al. |
August 28, 2008 |
ALKYLIDENE COMPLEXES OF RUTHENIUM CONTAINING N-HETEROCYCLIC CARBENE
LIGANDS; USE AS HIGHLY ACTIVE, SELECTIVE CATALYSTS FOR OLEFIN
METATHESIS
Abstract
The invention relates to a complex of ruthenium of the
structural formula I, ##STR00001## where X.sup.1 and X.sup.2 are
identical or different and are each an anionic ligand, R.sup.1 and
R.sup.2 are identical or different and can also contain a ring, and
R.sup.1 and R.sup.2 are each hydrogen or/and a hydrocarbon group,
the ligand L.sup.1 is an N-heterocyclic carbene and the ligand
L.sup.2 is an uncharged electron donor, in particular an
N-heterocyclic carbene or an amine, imine, phosphine, phosphate,
stibine, arsine, carbonyl compound, carboxyl compound, nitrile,
alcohol, ether, thiol or thioether, where R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are hydrogen or/and hydrocarbon groups. The invention
further relates to a process for preparing acyclic olefins having
two or more carbon atoms or/and cyclic olefins having four or more
carbon atoms from acyclic olefins having two or more carbon atoms
or/and from cyclic olefins having four or more carbon atoms by an
olefin metathesis reaction in the presence of at least one
catalyst, wherein a complex is used as catalyst and R'.sup.1,
R'.sup.2, R'.sup.3 and R'.sup.4 are hydrogen or/and hydrocarbon
groups.
Inventors: |
Herrmann; Wolfgang Anton;
(Freising, DE) ; Schattenmann; Wolfgang;
(Burghausen, DE) ; Weskamp; Thomas; (Munchen,
DE) |
Correspondence
Address: |
Connolly Bove Lodge & Hutz LLP
1007 North Orange Street, P.O. Box 2207
Wilmington
DE
19899-2207
US
|
Assignee: |
Evonik Degussa GmbH
Hanau
DE
|
Family ID: |
7863687 |
Appl. No.: |
12/115139 |
Filed: |
May 5, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11828828 |
Jul 26, 2007 |
7378528 |
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12115139 |
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11021967 |
Dec 23, 2004 |
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11828828 |
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10630552 |
Jul 29, 2003 |
7294717 |
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11021967 |
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09647742 |
Nov 27, 2000 |
6635768 |
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PCT/EP99/01785 |
Mar 18, 1999 |
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10630552 |
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Current U.S.
Class: |
548/103 ;
585/500 |
Current CPC
Class: |
B01J 2231/543 20130101;
B01J 2231/54 20130101; B01J 31/2404 20130101; B01J 31/2208
20130101; B01J 2231/14 20130101; B01J 31/2265 20130101; C07C 67/475
20130101; B01J 2531/0263 20130101; B01J 31/18 20130101; C08G 61/08
20130101; B01J 31/26 20130101; C07C 67/475 20130101; C07C 6/04
20130101; C07C 2531/24 20130101; C07C 67/313 20130101; B01J 31/2273
20130101; C07F 15/0046 20130101; C07C 6/04 20130101; C07C 2531/22
20130101; C07C 2/32 20130101; B01J 2531/821 20130101; C07C 6/04
20130101; C07C 67/313 20130101; C07C 13/20 20130101; C07C 69/593
20130101; C07C 11/02 20130101; C07C 69/593 20130101 |
Class at
Publication: |
548/103 ;
585/500 |
International
Class: |
C07F 15/00 20060101
C07F015/00; C07C 2/00 20060101 C07C002/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 6, 1998 |
DE |
DE 198 15 275.2 |
Claims
1. A complex of ruthenium of the structural formula I, ##STR00016##
where X.sup.1 and X.sup.2 are identical or different and are each
an anionic ligand, R.sup.1 and R.sup.2 are identical or different
and are each hydrogen of a hydrocarbon group, where the hydrocarbon
groups are identical or different and are selected independently
from among straight-chain, branched, cyclic or noncyclic radicals
from the group consisting of alkyl radicals having from 1 to 50
carbon atoms, alkenyl radicals having up to 50 carbon atoms,
alkynyl radicals having up to 50 carbon atoms, aryl radicals having
up to 30 carbon atoms and silyl radicals, or R.sup.1 and R.sup.2
form a ring, where one or more of the hydrogen atoms in the
hydrocarbon or silyl groups or both the hydrocarbon and silyl group
can be replaced independently by identical or different alkyl,
aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso,
hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or
sulfonyl groups, the ligand L.sup.1 is an N-heterocyclic carbene of
the formulae II-V and the ligand L.sup.2 is an N-heterocyclic
carbene of the formulae III-V or an amine, imine, phosphine,
phosphite, stibine, arsine, carbonyl compound, carboxyl compound,
nitrile, alcohol, ether, thiol or thioether, ##STR00017## where
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 in the formulae II, III, IV
and V are identical or different and are each hydrogen or a
hydrocarbon group, where the hydrocarbon groups comprise identical
or different, cyclic, noncyclic, straight-chain or/and branched
radicals selected from the group consisting of alkyl radicals
having from 1 to 50 carbon atoms, alkenyl radicals having up to 50
carbon atoms, alkynyl radicals having 1 up to 50 carbon atoms and
aryl radicals having up to 30 carbon atoms, in which at least one
hydrogen may be replaced by functional groups, and where one or
both of R.sup.3 and R.sup.4 may be identical or different halogen,
nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, thio or
sulfonyl groups.
2-3. (canceled)
4. A complex as claimed in claim 1, wherein R.sup.3 and R.sup.4 in
the formulae II, III, IV and V form a fused-on ring system.
5. A complex as claimed in claim 1, wherein L.sup.1 and L.sup.2
form a chelating ligand of the formula VI L.sup.1-Y-L.sup.2 VI
where the bridges Y comprise cyclic, noncyclic, straight-chain or
branched radicals selected from the group consisting of alkylene
radicals having from 1 to 50 carbon atoms, alkenylene radicals
having up to 50 carbon atoms, alkynylene radicals having up to 50
carbon atoms, arylene radicals having up to 30 carbon atoms,
metallocenylene, borylene and silylene radicals in which one or
more hydrogens may be replaced independently by identical or
different alkyl, aryl, alkenyl, alkynyl, metallocenyl, halo, nitro,
nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl,
carbonyl, thio or sulfonyl groups.
6. (canceled)
7. (canceled)
8. A process for preparing acyclic olefins having two or more
carbon atoms or cyclic olefins having four or more carbon atoms, in
each case of the formula VII ##STR00018## from acyclic olefins
having two or more carbon atoms or from cyclic olefins having four
or more carbon atoms, in each case corresponding to the formula VII
by an olefin metathesis reaction in the presence of at least one
catalyst comprising the complex as claimed in claim 1 and R'.sup.1,
R'.sup.2, R'.sup.3 and R'.sup.4 in the formula VII are hydrogen or
hydrocarbon groups, where the hydrocarbon groups are each selected
independently from among straight-chain, branched, cyclic or
noncyclic radicals of the group consisting of alkyl radicals having
from 1 to 50 carbon atoms, alkenyl radicals having up to 50 carbon
atoms, alkynyl radicals having up to 50 carbon atoms, aryl radicals
having up to 30 carbon atoms, metallocenyl or silyl radicals, in
which one or more hydrogens may be replaced by a functional group,
where one or more of R'.sup.1, R'.sup.2, R'.sup.3 and R'.sup.4 may
independently be identical or different halogen, nitro, nitroso,
hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio,
sulfonyl or metallocenyl groups.
9. (canceled)
10. The process as claimed in claim 8, wherein R'.sup.1, R'.sup.2,
R'.sup.3 and R'.sup.4 in the olefins of the formula VII to be
prepared form, in pairs, one or more identical or different
rings.
11.-16. (canceled)
Description
RELATED APPLICATIONS
[0001] This application is also a divisional of U.S. patent
application Ser. No. 11/021,967, filed Dec. 23, 2004, which is a
divisional of U.S. patent application Ser. No. 10/630,552, filed
Jul. 29, 2003, which is a divisional of U.S. patent application
Ser. No. 09/647,742, filed on Nov. 27, 2000, now U.S. Pat. No.
6,635,768, which was filed as a National stage (under 35 USC 371)
application of PCT/EP99/01785, filed on Mar. 18, 1999, which claims
benefit to German Application Number 198 15 275.2, filed Apr. 6,
1998.
[0002] The invention relates to alkylidene complexes of ruthenium
containing N-heterocyclic carbene ligands and a process for
preparing olefins by olefin metathesis from acyclic olefins having
two or more carbon atoms or/and from cyclic olefins having four or
more carbon atoms using at least one of these alkylidene complexes
as catalyst.
[0003] C-C coupling reactions catalyzed by transition metals are
among the most important reactions of organic synthetic chemistry.
In this context, olefin metathesis makes a significant
contribution, since this reaction enables by-product-free olefins
to be synthesized. Olefin metathesis has not only a high potential
in the area of preparative, organic synthesis (RCM, ethenolysis,
metathesis of acyclic olefins) but also in polymer chemistry (ROMP,
ADMET, alkyne polymerization). Since its discovery in the 1950s, a
number of industrial processes have been able to be realized.
Nevertheless, olefin metathesis has developed into a broadly
applicable synthetic method only recently due to the discovery of
new catalysts (J. C. Mol in: B. Cornils, W. A. Herfmann: Applied
Homogeneous Catalysis with Organometallic Compounds, VCH, Weinheim,
1996, p. 318-332; M. Schuster, S. Blechert, Angew. Chem. 1997, 109,
2124-2144; Angew, Chem. Int. Ed. Engl. 1997, 36, 2036-2056).
[0004] Numerous, fundamental studies have made important
contributions to the understanding of this transition
metal-catalyzed reaction in which an exchange of alkylidene units
between olefins occurs. The generally accepted mechanism involves
metal-alkylidene complexes as active species. These react with
olefins to form metallacyclobutane intermediates which undergo
cycloreversion to once again form olefins and alkylidene complexes.
The isolation of metathesis-active alkylidene and
metallacyclobutane complexes supports these mechanistic
hypotheses.
[0005] Numerous examples may be found, in particular, in the
coordination chemistry of molybdenum and tungsten. Specifically the
work of Schrock gave well-defined alkylidene complexes whose
reactivity can be controlled (J. S. Murdzek, R. R. Schrock,
Organometallics 1987, 6, 1373-1374). The introduction of a chiral
ligand sphere in these complexes made possible the synthesis of
polymers having a high tacticity (K. M. Totland, T. J. Boyd, G. C.
Lavoie, W. M. Davis, R. R. Schrock, Macromolecules 1996, 29,
6114-6125). Chiral complexes of the same structural type have also
been used successfully in ring-closing metathesis (O. Fujimura, F.
J. d. L. Mata, R. H. Grubbs, Organometallics 1996, 15, 1865-1871).
However, the high sensitivity toward functional groups, air and
water is a drawback.
[0006] Recently, phosphine-containing complexes of ruthenium have
become established (R. H. Grubbs, S. T. Nguyen, L. K. Johnson, M.
A. Hillmyer, G. C. Fu, WO 96/04289, 1994; P. Schwab, M. B. France,
J. W. Ziller, R. H. Grubbs, Angew. Chem., 1995, 107, 2119-2181;
Angew. Chem. Int. Ed. Engl. 1995, 34, 2039-2041). Owing to the
electron-rich, "soft" character of later transition metals, these
complexes have a high tolerance toward hard, functional groups.
This is demonstrated, for example, by their use in natural product
chemistry (RCM of dienes) (Z. Yang, Y. He, D. Vourloumis, H.
Vallberg, K. C. Nicolaou, Angew. Chem. 1997, 109, 170-172; Angew.
Chem., Int, Ed. Engl. 1997, 36, 166-168; D. Meng, P. Bertinato, A.
Balog, D. S. Su, T. Kamenecka, E. J. Sorensen, S. J. Danishefsky,
J. Am. Chem. Soc. 1997, 119, 2733-2734; D. Schinzer, A. Limberg, A.
Bauer, O. M. Bohm, M. Cordes, Angew. Chem. 1997, 109, 543-544;
Angew. Chem., Int. Ed. Engl. 1997, 36, 523-524; A; Furstner, K.
Langemann, J. Am. Chem. Soc. 1997, 119, 9130-9136).
[0007] However, the range of variation of the phosphine ligands
used is very restricted due to steric and electronic factors. Only
strongly basic, bulky alkylphosphines such as
tricyclohexylphosphine, triisopropylphosphine and
tricyclopentylphosphine are suitable for the metathesis of acyclic
olefins and relatively unstrained ring systems. Accordingly, the
reactivity of these catalysts cannot be adjusted. Chiral complexes
of this structural type have also not been able to be obtained.
[0008] For these reasons, it is an object of the invention to
develop tailored metathesis catalysts which have a high tolerance
toward functional groups as a result of a variable ligand sphere
and which allow fine adjustment of the catalyst for specific
properties of different olefins.
[0009] This object is achieved according to the invention by a
complex of ruthenium of the structural formula I,
##STR00002##
where X.sup.1 and X.sup.2 are identical or different and are each
an anionic ligand, R.sup.1 and R.sup.2 are identical or different
and can also contain a ring, and R.sup.1 and R.sup.2 are each
hydrogen or/and a hydrocarbon group, where the hydrocarbon groups
are identical or different and are selected independently from
among straight-chain, branched, cyclic or/and noncyclic radicals
from the group consisting of alkyl radicals having from 1 to 50
carbon atoms, alkenyl radicals having from 1 to 50 carbon atoms,
alkynyl radicals having from 1 to 50 carbon atoms, aryl radicals
having from 1 to 30 carbon atoms and silyl radicals, where one or
more of the hydrogen atoms in the hydrocarbon or/and silyl groups
can be replaced independently by identical or different alkyl,
aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso,
hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio
or/and sulfonyl groups, the ligand L.sup.1 is an N-heterocyclic
carbene of the formulae II-V and the ligand L.sup.2 is an uncharged
electron donor, in particular an N-heterocyclic carbene of the
formulae II-V or an amine, imine, phosphine, phosphite, stibine,
arsine, carbonyl compound, carboxyl compound, nitrile, alcohol,
ether, thiol or thioether,
##STR00003##
where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in the formulae II,
III, IV and V are identical or different and are each hydrogen
or/and a hydrocarbon group, where the hydrocarbon groups comprise
identical or different, cyclic, noncyclic, straight-chain or/and
branched radicals selected from the group consisting of alkyl
radicals having from 1 to 50 carbon atoms, alkenyl radicals having
from 1 to 50 carbon atoms, alkynyl radicals having from 1 to 50
carbon atoms and aryl radicals having from 1 to 30 carbon atoms, in
which at least one hydrogen may be replaced by functional groups,
and where one or both of R.sup.3 and R.sup.4 may be identical or
different halogen, nitro, nitroso, alkoxy, aryloxy, amido,
carboxyl, carbonyl, thio or/and sulfonyl groups.
[0010] The alkyl radicals, alkenyl radicals or allynyl radicals in
the formulae I to V preferably have from 1 to 20 carbon atoms,
particularly preferably from 1 to 12 carbon atoms.
BRIEF DESCRIPTION OF THE FIGURES
[0011] FIG. 1 illustrates the yield % versus t/min for compounds A
and B in a ring-opening metathesis polymerization of
1,5-cyclooctadiene and
[0012] FIG. 2 illustrates the yield % versus t/min for compounds A
and B in a ring-opening metathesis polymerization of
cyclooctene.
[0013] The complexes of the invention are highly active catalysts
for olefin metathesis. They are particularly inexpensive. In olefin
metathesis, the catalysts of the invention display not only a high
tolerance toward a variety of functional groups but also a wide
range of possible variations in the ligand sphere. Variation of the
preparatively readily obtainable N-heterocyclic carbene ligands
enables activity and selectivity to be controlled in a targeted
manner and, in addition, chirality can be introduced in a simple
way.
[0014] The anionic ligands X.sup.1 and X.sup.2 of the complex of
the of invention, which are identical or different, are preferably
each halide, pseudohalide, tetraphenylborate, perhalogenated,
tetraphenylborate, tetrahaloborate, hexahalophosphate,
hexahaloantimonate, trihalomnethanesulfonate, alkoxide,
carboxylate, tetrahaloaluminate, tetracarbonylcobaltate,
hexahaloferrate (ITT), tetrahaloferrate (III) or/and
tetrahalopalladate (II), with preference being given to halide,
pseudohalide, tetraphenylborate, perfluorinated tetraphenylborate,
tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate,
trifluorotnethanesulfonate, alkoxide, carboxylate,
tetrachloroaluminate, tetracarbonylcobaltate, hexafluoroferrate
(III) tetrachloroferrate (III) or/and tetrachloropalladate (II) and
preferred pseudohalides being cyanide, thiocyanate, cyanate,
isocyanate and isothiocyanate.
[0015] In the formulae II, III, IV and V, some or all of the
hydrogen in the hydrocarbon groups R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 can be replaced independently by identical or different
halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido,
carboxyl, carbonyl, thio, sulfonyl or/and metallocenyl groups. In
these formulae, R.sup.3 and R.sup.4 can form a fused-on ring
system.
[0016] The ligands L.sup.1 and L.sup.2 of the complex of the
structural formula I can form a chelating ligand of the formula
VI
L.sup.1-Y-L.sup.2 VI
where the bridges Y can comprise cyclic, noncyclic, straight-chain
or/and branched radicals selected from the group consisting of
alkylene radicals having from 1 to 50 carbon atoms, alkenylene
radicals having from 1 to 50 carbon atoms, alkynylene radicals
having from 1 to 50 carbon atoms, arylene radicals having from 1 to
30 carbon atoms, metallocenylene, borylene and silylene radicals in
which one or more hydrogens may be replaced independently by
identical or different alkyl, aryl, alkenyl, alkynyl, metallocenyl,
halo, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido,
carboxyl, carbonyl, thio or/and sulfonyl groups, preferably alkyl,
aryl or/and metallocenyl groups.
[0017] The ligands of the formulae II, III, IV, V or/and VI can
have central, axial or/and planar chirality.
[0018] In the structural formula I of the complex, R.sup.1 and
R.sup.2 are preferably hydrogen, substituted or/and unsubstituted
alkyl, alkenyl or/and aryl radicals, X.sup.1 and X.sup.2 are
preferably halide, alkoxide or/and carboxylate ions and L.sup.1 and
L.sup.2 are preferably each an N-heterocyclic carbene of the
formula II.
[0019] The complexes are usually synthesized by ligand replacement
in corresponding phosphine complexes. Two phosphine ligands can be
replaced selectively in accordance with the reaction equation (1)
or only one can be replaced in accordance with reaction equation
(2). In the case of single replacement, the second phosphine can be
replaced selectively by another electron donor, e.g. pyridine,
phosphine, N-heterocyclic carbene, phosphate, stibene, arsine, in
accordance with reaction equation (3).
[0020] In particular, this route makes it possible for the first
time to prepare chiral, metathesis-active catalysts based on
ruthenium (example complexes 2 and 3).
##STR00004##
[0021] The complexes of the invention are found to be extremely
efficient catalysts in olefin metathesis. The excellent metathesis
activity is demonstrated in the examples by means of a number of
examples of different metathesis reactions.
[0022] The present invention therefore also encompasses processes
for all olefin metathesis reactions such as ring-opening metathesis
polymerization (ROMP), metathesis of acyclic olefins, ethenolysis,
ring-closing metathesis (RCM), acyclic diene metathesis
polymerization (ADMET) and depolymerization of olefin polymers. The
high stability and tolerance of the complexes of the invention
toward functional groups; in particular alcohol, amine, thiol,
ketone, aldehyde, carboxylic acid, ester, amide, ether, silane,
sulfide and halogen groups, makes it possible for such functional
groups to be present during the metathesis reaction.
[0023] The object of the invention is also achieved by a process
for preparing acyclic olefins having two or more carbon atoms
or/and cyclic olefins having four or more carbon atoms, in each
case of the formula VII
##STR00005##
VII
[0024] from acyclic olefins having two or more carbon atoms or/and
from cyclic olefins having four or more carbon atoms, in each case
corresponding to the formula VII by an olefin metathesis reaction
in the presence of at least one catalyst, wherein a catalyst as
claimed in any one of claims 1 to 7 is used and R'.sup.1, R'.sup.2,
R'.sup.3 and R'.sup.4 in the formula VII are hydrogen or/and
hydrocarbon groups, where the hydrocarbon group is each selected
independently from among straight-chain, branched, cyclic or/and
noncyclic radicals of the group consisting of alkyl radicals having
from 1 to 50 carbon atoms, alkenyl radicals having from 1 to 50
carbon atoms, alkynyl radicals having from 1 to 50 carbon atoms,
aryl radicals having from 1 to 30 carbon atoms, metallocenyl or/and
silyl radicals, in which one or more hydrogens may be replaced by a
functional group, where one or more of R'.sup.1, R'.sup.2, R'.sup.3
and R'.sup.4 may independently be identical or different halogen,
nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl,
carbonyl, thio, sulfonyl or/and metallocenyl groups.
[0025] The olefins used preferably contain one or more double
bonds. In particular, R'.sup.1, R'.sup.2, R'.sup.3 and R'.sup.4 in
the olefins of the formula VII to be prepared form, in pairs, one
or more identical or different rings.
[0026] Preferably, some or all of the hydrogen atoms in the
hydrocarbon groups R'.sup.1, R'.sup.2, R'.sup.3 and R'.sup.4 of the
olefins of the formula VII to be prepared are replaced
independently by identical or different halogen, silyl, nitro,
nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl,
carbonyl, thio, sulfonyl or/and metallocenyl groups.
[0027] The process of the invention can be carried out in the
presence or absence of solvents, but preferably in the presence of
organic solvents. The process of the invention can advantageously
be carried out with addition of a Bronsted acid, preferably HCl,
HBr, HI, HBF.sub.4, HPF.sub.6 or/and trifluoroacetic acid, or/and
with addition of a Lewis acid, preferably BF.sub.3, AlCl.sub.3
or/and ZnI.sub.2.
[0028] Surprisingly, this makes it possible for the first time to
tailor a wide variety of olefins individually to different
properties on the basis of small variations in the catalysis
conditions or/and the catalysts, since the process of the invention
for preparing olefins has an unexpectedly high tolerance toward
functional groups.
EXAMPLES
[0029] The following examples illustrate the invention but do not
restrict its scope.
1) Preparation of the Complex of the Invention
General Procedure:
[0030] 1 mmol of (PPh.sub.3).sub.2Cl.sub.2Ru(.dbd.CHPh) was
dissolved in 20 ml of toluene and admixed with a solution of 2.2
equivalents of the appropriate imidazolin-2-ylidene in 5 ml of
toluene. The reaction solution was stirred at room temperature RT
for 45 minutes, subsequently evaporated to about 2 ml and the crude
product was precipitated using 25 ml of pentane. The crude product
was taken up in 2 ml of toluene and precipitated using 25 ml of
pentane a number of times. The residue was extracted with toluene,
the solution was evaporated to dryness, washed twice with pentane
and dried for a number of hours in a high vacuum.
[0031] The data from low-temperature NMR spectra are mostly
reported for characterization, since the spectra at room
temperature sometimes did not give all the information because of
dynamic effects.
[0032] The following compounds are prepared by the above described
general procedure:
1a)
Benzylidenedichlorobis(1,3-diisopropylimidazolin-2-ylidene)ruthenium
[0033] complex 1:
[0034] Yield: 487 mg (0.86 mmol=86% of theory)
[0035] Elemental analysis EA for C.sub.25H.sub.3Cl.sub.2N.sub.4Ru
(566.58)
[0036] found C, 53.21; H, 6.83; N, 9.94.
[0037] calculated C, 53.00; H, 6.76; N, 9.89.
[0038] .sup.1H-NMR (CD.sub.2Cl.sub.2/200 K); .delta. 20.33 (1H, s,
Ru.dbd.CH), 8.25 (2H, d, .sup.3J.sub.HH=7.6 Hz, o-H of
C.sub.6H.sub.5), 7.63 (1H, t, .sup.3J.sub.HH=7.6 Hz, p-H of
C.sub.6H.sub.5), 7.34 (2H, t, m-H of C.sub.6H.sub.5,
.sup.3J.sub.HH=7.6 Hz), 7.15 (2H, br, NCH), 7.03 (2H, br, NCH),
5.97 (2H, spt, .sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 3.73 (2H, spt,
.sup.3J.sub.HH=6.4 Hz, NCEMe.sub.2), 1.64 (12H, d,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 1.11 (6H, d,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 0.75 (6H, d,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2).
[0039] .sup.13C-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 295.6
(Ru.dbd.CH), 183.5 (NCN), 151.6 (ipso-C of C.sub.6H.sub.5), 129.5,
128.6 and 128.1 (o-C, m-C and p-C of C.sub.6H.sub.5), 118.1 and
117.2 (NCH), 52.1 and 50.1 (NCHMe.sub.2), 24.5, 23.8, 23.8 and 22.4
(NCHMe.sub.2).
1b)
Benzylidenedichlorobis(1,3-di((R)-1'-phenylethyl)-imidazolin-2-yliden-
e)ruthenium [0040] complex 2:
[0041] Yield: 676 mg (0.83 mmol=83% of theory)
[0042] EA for C.sub.45H.sub.46Cl.sub.2N.sub.4Ru(814.86):
[0043] found C, 66.48; H, 5.90; N, 6.73.
[0044] calc. C, 66.33; H, 5.69; N, 6.88.
[0045] .sup.1H-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 20.26 (1H, s,
Ru.dbd.CH), 8.13 (2H, br, o-H C.sub.6H.sub.5), 7.78-6.67 (29H, of
which 2m-H and 1p-H of C.sub.6H.sub.5, 20H of NCHMePh, 2H of
NCHMePh and 4H of NCH), 4.91 (2H, m, NCHMePh) 1.84 (3H, d,
.sup.3J.sub.HH=6.6 Hz, NCHMePh), 1.81 (3H, d, .sup.3J.sub.HH=6.6
Hz, NCHMePh), 1.51 (3H, d, .sup.3J.sub.HH=6.6 Hz, NCHMePh), 1.21
(3H, d, .sup.3J.sub.HH=6.6 Hz, NCHMePh).
[0046] .sup.13C-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 294.7
(Ru.dbd.CH), 186.0 and 185.6 (NCN), 151.2 (ipso-C of
C.sub.6H.sub.5), 141.2, 140.3, 140.1 and 139.9 (ipso-C of NCHMePh),
133.1-125.9 (o-C, m-C, p-C of C.sub.6H.sub.5 and NCHMePh), 120.5,
119.9, 119.2 and 118.8 (NCH), 57.6, 57.4, 56.7 and 56.1 (NCHMePh),
22.2, 20.6, 20.4 and 20.3 (NCHMePh).
1c)
Benzylidenedichlorobis(1,3-di-((R)-1'-naphthyl-ethyl)imidazolin-2-yli-
dene)ruthenium [0047] complex 3:
[0048] Yield: 792 mg (0.78 mmol=78% of theory)
[0049] EA for C.sub.61H.sub.54Cl.sub.2N.sub.4Ru(1015.1):
[0050] found C, 72.34; H, 5.46; N, 5.45.
[0051] calc. C, 72.18; H, 5.36; N, 5.52.
[0052] .sup.1H-NMR (CD.sub.2Cl.sub.2/260 K): .delta. 20.90 (1H, s,
Ru.dbd.CH), 8.99 (2H, br, o-H of C.sub.6H.sub.5), 8.2-5.6 (39H, of
which 2 nm-H and 1p-H of C.sub.6H.sub.5, 28H of NCHMeNaph, 41 of
NCH and 41 of NCRMeNaph), 2.5-0.8 (12H, m, NCHMeNaph).
[0053] .sup.13C-NMR (CD.sub.2Cl.sub.2/260 K): .delta. 299.9
(Ru.dbd.CH), 187.2 and 184.7 (NCN), 152.0 (ipso-C of
C.sub.6H.sub.5), 136.0-124.0 (o-C, m-C, p-C of C.sub.6H.sub.5 and
NCHMeNaph), 121.7, 121.0, 119.9, and 118.9 (NCH), 56.7, 56.1, 55.0
and 54.7 (NCHMeNaph), 24.7, 24.3, 21.0 and 20.0 (NCHMeNaph).
[0054] For the following complexes, slight deviations from the
general procedure are necessary:
1d)
(4-Chlorobenzylidene)dichlorobis(1,3-duisopropy-limidazolin-2-ylidene-
)ruthenium [0055] complex 4:
[0056] 1 mmol of
(Ph.sub.3).sub.2Cl.sub.2Ru[.dbd.CH(p-C.sub.6H.sub.4Cl)] was used as
starting material. The further procedure corresponded to the above
described general procedure.
[0057] Yield: 535 mg (0.89 mmol=89% of theory)
[0058] EA for C.sub.24H.sub.38Cl.sub.3N.sub.4Ru (601.03)
[0059] found C, 48.13; H, 6.33; N, 9.24.
[0060] calc. C, 47.96; H, 6.37; N, 9.32.
[0061] .sup.1H-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 20.33 (1H, s,
Ru.dbd.CH), 8.25 (2H, d, .sup.3J.sub.HH=7.6 Hz, o-H of
C.sub.6H.sub.4Cl), 7.63 (1H, t, .sup.3J.sub.HH=7.6 Hz, m-H of
C.sub.6H.sub.4Cl), 7.15 (2H, br, NCH), 7.03 (2H, br, NCH), 5.97
(2H, spt, .sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 3.73 (2H, spt,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 1.64 (12H, d,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 1.11 (6H, d,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2), 0.75 (6H, d,
.sup.3J.sub.HH=6.4 Hz, NCHMe.sub.2).
[0062] .sup.13C-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 295.6
(Ru.dbd.CH), 183.5 (NCN), 151.6 (ipso-C of C.sub.6H.sub.4Cl), 134.3
(p-C of C.sub.6H.sub.4Cl), 128.6 and 128.1 (o-C and m-C of
C.sub.6H.sub.4Cl), 118.1 and 117.2 (NCH), 52.1 and 50.1
(NCHMe.sub.2), 24.5, 23.8, 23.8 and 22.4 (NCHMe.sub.2).
1e)
Benzylidenedichlorobis(1,3-dicyclohexylimidazolin-2-ylidene)ruthenium
[0063] complex 5:
[0064] 1 mmol of (PPh.sub.3).sub.2Cl.sub.2Ru(.dbd.CHPh) was
dissolved in 25 ml of toluene and admixed with a solution of 2.2
equivalents of 1,3-dicyclohexylimidazolin-2-ylidene in 5 ml of
toluene. The reaction solution was stirred at RT for 45 minutes and
subsequently freed of the solvent. Unlike the general procedure,
the crude product was purified by flash chromatography.
[0065] Yield: 305 mg (0.42 mmol=42% of theory)
[0066] EA for C.sub.37H.sub.54Cl.sub.2N.sub.4Ru (726.84):
[0067] found C, 61.23; H, 7.56; N, 7.87.
[0068] calc. C, 61.14; H, 7.49; N, 7.71.
[0069] .sup.1H-NMR (CD.sub.2Cl.sub.2/298 K): a 20.45 (1H, s,
Ru.dbd.CH), 8.31 (2H, d, .sup.3J.sub.HH=7.6 Hz, O--H-- of
C.sub.6H.sub.5), 7.63 (1H, t, .sup.3J.sub.HH=7.6 Hz, p-H-- of
C.sub.6H.sub.5), 7.34 (2H, t, .sup.3J.sub.HH=7.6 Hz, m-H-- of
C.sub.6H.sub.5), 7.14 (2H, br, NCH), 7.00 (2H, br, NCH), 6.06 (2H,
br, CH of NC.sub.6H.sub.11), 3.82 (2H, br, CH of NC.sub.6H.sub.11),
1.64 (12H, br, CH.sub.2 of NC.sub.6H.sub.11), 0.93 (12H, br,
CH.sub.2 of NC.sub.6H.sub.11).
[0070] .sup.13C-NMR (CD.sub.2Cl.sub.2/298 K): .delta. 299.4
(Ru.dbd.CH), 182.9 (NCN), 152.0 (ipso-C of C.sub.6H.sub.5), 131.1,
129.8 and 129.1 (o-C, m-C and p-C of C.sub.6H.sub.5), 118.3 and
117.8 (br, NCH), 59.6 and 57.5 (br, CH of NC.sub.6H.sub.11), 35.7,
26.9 and 25.6 (br, CH.sub.2 of NC.sub.6H.sub.11).
1f)
Benzylidenedichloro(1,3-di-tert-butylimidazolin-2-ylidene)(triphenylp-
hosphine)ruthenium [0071] complex 6:
[0072] 1 mmol of (PPh.sub.3).sub.2Cl.sub.2Ru(.dbd.CHPh) was
dissolved in 20 ml of toluene and admixed with a solution of 1.1
equivalents of 1,3-di-tert-butylimidazolin-2-ylidene in 5 ml of
toluene. The reaction solution was stirred at RT for 30 minutes,
subsequently evaporated to about 2 ml and the crude product was
precipitated using 25 ml of pentane. The further work-up was
carried out as described in the general procedure.
[0073] Yield. 493 mg (0.70 mmol=70% of theory)
[0074] EA for C.sub.36H.sub.41Cl.sub.2N.sub.2P.sub.1Ru
(704.69):
[0075] found C, 61.12; H, 5.55; N, 3.62; P, 4.59.
[0076] calc. C, 61.36; H, 5.86; N, 3.98; P, 4.38.
[0077] .sup.1H-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 20.70 (1H, s,
Ru.dbd.CH), 8.03 (2H, d, .sup.3J.sub.HH=7.6 Hz, c-H of
C.sub.6H.sub.5), 7.50-6.95 (20H, of which 2m-H and 1p-H of
C.sub.6H.sub.5, 15H of PPh.sub.3 and 2H of NCH), 1.86 (9H, s,
NCMe.sub.3), 1.45 (9H, 5, NCMe.sub.3).
[0078] .sup.13C-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 307.4 (br,
Ru.dbd.CH), 178.3 (d, J.sub.PC=86 Hz, NCN), 151.5 (d, J.sub.PC=4.5
Hz, ipso-C of C.sub.6H.sub.5), 135.0 (m, o-C of PPh.sub.3), 131.9
(m, ipso-C of PPh.sub.3), 130.2 (s, p-C of PPh.sub.3), 129.5, 128.6
and 128.1 (s, o-C, m-C and p-C of C.sub.6H.sub.5), 128.0 (m, m-C of
PPh.sub.3), 117.7 and 117.6 (NCH), 58.7 and 58.5 (NCMe.sub.3), 30.0
and 29.5 (NCMe.sub.3).
[0079] .sup.31P-NMR (CD.sub.2Cl.sub.2/200 K): .delta. 40.7 (s,
PPh.sub.3).
1g)
Benzylidenedichloro-(1,3-dicyclohexylimidazolin-2-ylidene)(tricyclohe-
xylphosphine)ruthenium
##STR00006##
[0080] A solution of 1.2 mmol of dicyclohexylimidazolin-2-ylidene
is added dropwise at -78.degree. C. to 1 mmol of
RuCl.sub.2(PCy.sub.3).sub.2(CHPh) in 100 ml of THF. The mixture is
slowly warmed to room temperature over a period of 5 hours and the
solvent is subsequently removed. The crude product is extracted
with a mixture of 2 ml of toluene and 25 ml of pentane and the
product is precipitated from this solution at -78.degree. C.
[0081] Yield: 0.80 mmol (80% of theory)
[0082] EA for C.sub.40H.sub.63Cl.sub.2N.sub.2PRu:
[0083] found C, 61.99; H, 8.20; N, 3.62; calc. C, 61.11; H, 8.29;
N, 3.59.
[0084] .sup.1H NMR (CD.sub.2Cl.sub.2/25.degree. C.) .delta.=20.30
(1H, d, .sup.3J.sub.PH=7.4 Hz, Ru.dbd.CH), 8.33 (2H, d,
.sup.3J.sub.PH=7.4 Hz, o-H of C.sub.6H.sub.5), 7.62 (1H, t,
.sup.3J.sub.HH=7.4 Hz, p-H of C.sub.6H.sub.5), 7.33 (2H, t,
.sup.3J.sub.HH=7.4 H.sub.2, o-H of C.sub.6H.sub.5), 7.11 (1H, s,
NCH), 6.92 (1H, s, NCH), 5.97 (1H, m, CH of NC.sub.6H.sub.11), 3.36
(1H, m, CH of NC.sub.6H.sub.11), 2.42 (3H, m, CH of PCy.sub.3),
1.90-0.89 (50H, all m, CH.sub.2 of NC.sub.6H.sub.11 and
PCy.sub.3).
[0085] .sup.13C NMR (CD.sub.2Cl.sub.2/25.degree. C.): d=298.7
(Ru.dbd.CH), 181.2 (d, J.sub.PC=88 Hz, NCN), 152.5 (ipso-C of
C.sub.6H.sub.5), 130.8, 129.8, and 129.2 (o-C, m-C, and p-C of
C.sub.6H.sub.5), 118.9 and 118.0 (NCH), 59.5 and 57.7 (CH of
NC.sub.6H.sub.11) 33.2 (d, J.sub.PC=17 Hz, ipso-C of PCy.sub.3),
29.9 (s, m-C of PCy.sub.3), 26.8 (d, J.sub.PC=3.7 Hz, o-C of
PCy.sub.3), 25.4 (s, p-C of PCy.sub.3) 34.9, 33.3, 33.1, 28.2,
28.1, and 25.7 (CH.sub.2 of NC.sub.6H.sub.11).
[0086] .sup.31P NMR (CD.sub.2Cl.sub.2/25.degree. C.) d=28.2.
1h)
Benzylidenedichloro(1,3-di-((R)-1'-phenylethyl)-imidazolin-2-ylidene)-
(tricyclohexylphosphine)ruthenium
##STR00007##
[0087] A solution of 1.2 mmol of
di-(R)-1'-phenylethylimidazolin-2-ylidene is added dropwise at
-78.degree. C. to 1 mmol of RuCl.sub.2(PCy.sub.3).sub.2(CHPh) in
100 ml of THF. The mixture is slowly warmed to room temperature
over a period of 5 hours and the solvent is subsequently removed.
The crude product is extracted with a mixture of 2 ml of toluene
and 25 ml of pentane and the product is precipitated from this
solution at -78.degree. C.
[0088] Yield: 0.74 mmol (74% of theory)
[0089] EA for C.sub.44H.sub.59Cl.sub.2N.sub.2PRu:
[0090] calc. C, 64.53; H, 7.27; N, 3.42. found C, 64.58; H, 7.34;
N, 3.44.
[0091] .sup.1H NMR (CD.sub.2Cl.sub.2/25.degree. C.): d 20.19 (1H,
d, .sup.3J.sub.PH=4.5 Hz, Ru.dbd.CH), 7.74-7.00 (15H, all m, CH of
C.sub.6H.sub.5), (1H, m, NCHMePh), 6.73 (1H, s, NCH), 6.70 (1H, s,
NCH), 2.52 (1H, m, NCHMePh), 2.44 (3H, m, CH of PCy.sub.3), 2.11
(3H, d, .sup.3J.sub.HH=6.8 Hz, NCHMePh), 1.82-1.12 (3H, all ma, CH
of PCy.sub.3) 1.35 (3H, d, .sup.3J.sub.HH=6.8 Hz, NCHMePh).
[0092] .sup.13C NMR (CD.sub.2Cl.sub.2/25.degree. C.): .delta.=292.7
(Ru.dbd.CH), 183.4 (dr J.sub.PC=78 Hz, NCN), 151.8 (ipso-C of
C.sub.6H.sub.5), 140.1 and 139.5 (ipso-C of NCHMEPh), 129.5, 128.5,
128.3, 127.9, 127.5, 127.4, 127.2, 126.6, and 126.1 (o-C, m-C and
p-C of C.sub.6H.sub.5) 119.8 and 118.4 (NCH), 57.4 and 56.2
(NCHMePh), 31.3 (d, J.sub.PC=17 Hz, ipso-C of PCy.sub.3), 29.0 (s,
m-C of PCy.sub.3), 28.9 (s, m-C of PCy.sub.3), 27.2 (d,
J.sub.PC=3.7 Hz, o-C of PCy.sub.3), 27.0 (d, J.sub.PC=3.7 Hz, o-C
of PCy.sub.3), 25.8 (s, p-C of PCy.sub.3) 21.7 and 20.3
(NCHMePh).
[0093] .sup.31P NMR (CD.sub.2Cl.sub.2/25.degree. C.): .delta.
38.1.
1i)
Benzylidenedichloro(1,3-di-((R)-1'-naphthylethyl)-imidazolin-2-yliden-
e)(tricyclohexylphosphine)ruthenium
##STR00008##
[0094] A solution of 1.2 mmol of
d-(R)-1-naphthylethylimidazolin-2-ylidene is added dropwise at
-78.degree. C. to 1 mmol of RuCl.sub.2(PCy.sub.3).sub.2(CHPh) in
100 ml of THF. The mixture is slowly warmed to room temperature
over a period of 5 hours and the solvent is subsequently removed.
The crude product is extracted with a mixture of 2 ml of toluene
and 25 ml of pentane and the product is precipitated from this
solution at -78.degree. C.
[0095] Yield: 0.72 mmol (72% of theory)
[0096] EA for C.sub.52H.sub.63Cl.sub.2N.sub.2PRu:
[0097] calc. C, 67.95; H, 6.91; N, 3.05. found C, 68.09; H, 7.02;
N, 3.04.
[0098] .sup.1H NMR (CD.sub.2Cl.sub.2/25.degree. C.: .delta. 20.33
(1H, d, .sup.3J.sub.HH=5.4 Hz, Ru.dbd.CH), 8.88 (2H, d,
.sup.3J.sub.HH=8.0 Hz, o-H of C.sub.6H.sub.5) 7.94-6.96 (17 Hr all
m, CH of C.sub.6H.sub.5), 6.70 (1H, s, NCH), 6.61 (1H, s,
NCH).sub.r 5.83 (1H, m, NCHMeNaph), 2.59 (1H, m, NCHMeNaph), 2.49
(3H, m, CH of PCy.sub.3), 2.44 (3H, d, .sup.3J.sub.HH=6.8 Hz,
NCHMeNaph), 1.95-1.01 (3H, all m, CH.sub.2 of PCy.sub.3) 1.54 (3H,
d, .sup.3J.sub.HH=6.8 Hz, NCHMeNaph).
[0099] .sup.13C NMR (CD.sub.2Cl.sub.2/25.degree. C.): .delta.=298.4
(Ru.dbd.CH) 184.0 (d, J.sub.PC=87 Hz, NCN), 152.3 (ipso-C of
C.sub.6H.sub.5), 138.3 and 137.6 (ipso-C of NCHMeNaph), 134.3-122.9
(o-C, m-C, and p-C of C.sub.6H.sub.5, CHMeNaph) 120.6 and 119.5
(NCH), 56.4 and 55.7 (NCHMeNaph), 32.5 (d, J.sub.PC=17 Hz, ipso-C
of PCy.sub.3), 30.1 (s, M-C of PCy.sub.3), 30.0 (s, m-C of
PCy.sub.3), 28.1 (pseudo-t, J.sub.PC=7.4 Hz, o-C of PCy.sub.3),
26.8 (s, p-C of PCy.sub.3) 24.0 and 22.7 (NCHMeNaph).
[0100] .sup.31P NMR (CD.sub.2Cl.sub.2/25.degree. C.)
.delta.=31.8.
2) Use of the Complex of the Invention in Olefin Metathesis
[0101] The following examples demonstrate the potential of the
complexes of the invention in olefin metathesis. The advantage of
these complexes of the invention compared to phosphine-containing
complexes is the targeted and inexpensive variation of the radicals
R on the nitrogen atoms of the N-heterocyclic carbene ligands. This
tailoring of the catalysts of the invention on the basis of
individual properties of the olefins to be subjected to metathesis
enables both activity and selectivity of the reaction to be
controlled.
2a) Ring-Opening Metathesis Polymerization (ROMP):
[0102] Norbornene, cyclooctene and functionalized norbornene
derivatives serve as examples.
##STR00009##
Typical Reaction Procedure for the Polymerization of Cyclooctene
(or Norbornene):
[0103] 410 .mu.l (3.13 mmol) of cyclooctene were added to a
solution of 3.6 mg (6.3 .mu.mol) of 1 in 0.5 ml of methylene
chloride. After about 10 minutes, a highly viscous gel which could
no longer be stirred had formed. 1 ml of methylene chloride was
added. This procedure was repeated whenever the stirrer was no
longer able to operate (a total of 3 ml of methylene chloride).
After 1 hour, 5 ml of methylene chloride to which small amounts of
tert-butyl ether and 2,6-di-tert-butyl-4-methylphenol had been
added were introduced. After a further 10 minutes, the solution was
slowly added dropwise to a large excess of methanol, the mixture
was filtered and the solid was dried in a high vacuum for a number
of hours.
[0104] Yield: 291 mg (2.64 mmol=84.3% of theory)
TABLE-US-00001 TABLE 1 Polymerization of norbornene and cyclooctene
Ratio of [monomer]/ Reaction Example Complex Monomer [cat.] time t
Yield 2.1a 1 Norbornene 100:1 1 min 91% 2.1b 5 Norbornene 100:1 1
min 92% 2.1c 1 Cyclooctene 500:1 1 h 84% 2.1d 1 Cyclooctene 500:1 2
h 97% 2.1e 5 Cyclooctene 500:1 1 h 87%
Typical Reaction Procedure for the Polymerization of Functionalized
Norbornene Derivatives:
[0105] The formula VIII shows the basic skeleton of the norbornene
derivatives used in Table 2.
##STR00010##
[0106] 0.3 ml of a solution of 432 mg (3.13 mmol) of
5-carboxyl-2-norbornene (formula VIII with R.dbd.CO.sub.2H) in
methylene chloride was added to a solution of 3.6 mg (6.3 .mu.mol)
of 1 in 0.2 ml of methylene chloride. After about 10 minutes, a
highly viscous gel which could no longer be stirred had formed. A
further 0.5 ml of methylene chloride was added. This procedure was
repeated whenever the stirrer was no longer able to operate. After
1 hour, 5 ml of methylene chloride to which small amounts of
tert-butyl ether and 2,6-di-tert-butyl-4-methylphenol had been
added were introduced. After a further 10 minutes, the solution was
slowly added dropwise to a large excess of methanol, filtered and
the solid was dried in a high vacuum for a number of hours.
[0107] Yield: 423 mg (3.06 mmol=98.1% of theory)
[0108] The reactions at 50.degree. C. were carried out in an
analogous manner in dichloroethane instead of methylene
chloride.
TABLE-US-00002 TABLE 2 Polymerization of functionalized norbornene
derivatives Radical R in formula Reaction Example Complex VIII
T[.degree. C.] time t Yield 2.1f 1 O.sub.2CCH.sub.3 25 30 min 99%
2.1g 1 CH.sub.2OH 25 2 h 15% 2.1h 1 CH.sub.2OH 50 2 h 18% 2.1i 1
CHO 25 2 h 36% 2.1k 1 CHO 50 2 h 52% 2.1l 1 COCH.sub.3 25 2 h 42%
2.1m 1 COCH.sub.3 50 2 h 67% 2.1n 1 CO.sub.2H 25 2 h 98%
[0109] The polymerization of norbornene occurred in seconds. In the
polymerization of cyclooctene, virtually quantitative conversions
were obtained within one hour (Table 1). Differences in activity
can be detected by use of various complexes under dilute conditions
and demonstrate the dependence of the activity on the substitution
pattern of the carbene ligands used. The high stability and
tolerance toward functional groups is demonstrated by the
polymerization of functionalized norbornene derivatives containing
ester, alcohol, aldehyde, ketone or/and carboxylic acid groups
(Table 2). Here, monomers of the formula VIII with
R.dbd.CH.sub.2OH, CHO and CO.sub.2H were able to be polymerized for
the first time.
2.2) Ring-Closing Metathesis (RCM) of 1,7-octadiene:
##STR00011##
Typical Reaction Procedure for PCM of 1,7-octadiene:
[0110] A solution of 3.6 mg (6.3 .mu.mol) of 1 in 2 ml of
dichloroethane was admixed with 46 .mu.l (0.31 mmol) of
1,7-octadiene, and the reaction mixture was placed in an oil bath
at 60.degree. C. After one hour, the reaction mixture was analyzed
by GC/MS.
TABLE-US-00003 TABLE 3 RCM of 1,7-octadiene (octadiene/catalyst =
50:1) Reaction Example Complex Solvent T[.degree. C.] time t Yield
2.2a 1 Methylene chloride 25 5.5 h 51% 2.2b 1 Methylene chloride 25
24 h 70% 2.2c 1 Dichloroethane 60 1 h 99% 2.2d 2 Dichloroethane 60
1 h 99% 2.2e 3 Dichloroethane 60 1 h 99% 2.2f 5 Dichloroethane 60 1
h 99%
[0111] The potential in ring-closing metathesis was illustrated by
the reaction of 1,7-octadiene to form cyclohexene with liberation
of ethylene (Table 3). 1 gave a yield of 51% after 5.5 hours; at
60.degree. C., all complexes of the invention used gave
quantitative conversions.
2.3) Metathesis of Acyclic Olefins
[0112] A) Metathesis of 1-octene:
##STR00012##
Typical Reaction Procedure for the Metathesis of 1-octene:
[0113] A solution of 3.6 mg (6.3 .mu.mol) of 1 in 2 ml of
dichloroethane was admixed with 49 .mu.l (0.31 mmol) of 1-octene,
and the reaction mixture was placed in an oil bath at 60.degree. C.
After 3 hours, the reaction mixture was analyzed by GC/MS.
TABLE-US-00004 TABLE 4 Homometathesis of 1-octene (octene/catalyst
= 50:1) Reaction Conversion Example Complex T[.degree. C.] time t
of 1-octene Selectivity.sup.a 2.3a 2 60 1 h 31% 98% 2.3b 2 60 2 h
58% 97% 2.3c 1 60 1 h 83% 73% 2.3d 1 60 3 h 97% 63% .sup.aThe
selectivity indicates the proportion of 7-tetradecene compared to
other metathesis products
B) Metathesis of Methyl Oleate:
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[0114] Typical Reaction Procedure for the Metathesis of Methyl
Oleate:
[0115] A solution of 3.6 mg (6.3 .mu.mol) of 1 in 0.5 ml of
dichloroethane was admixed with 1.06 ml (3.13 mmol) of methyl
oleate, and the reaction mixture was placed in an oil bath at
60.degree. C. for 15 hours. GC/MS analysis indicated the
equilibrium of metathesis products shown in the reaction equation
(7).
[0116] The metathesis of terminal and internal olefins was
demonstrated by means of the homometathesis of 1-octene and methyl
oleate. In the metathesis of methyl oleate as natural raw material,
the thermodynamic equilibrium can virtually be reached within 15
hours using catalyst at an olefin:catalyst ratio of 500:1. In the
metathesis of 1-octene, 7-tetradecene was not obtained as sole
reaction product in all cases. An isomerization of 1-octene to
2-octene detected by NMR spectroscopy and subsequent olefin
metathesis is responsible for this fact. Homometathesis and
cross-metathesis of 1-octene and 2-octene gave not only
7-tetradecene but also 6-tridecene as main by-product and small
amounts of 6-dodecene, 1-heptene and 2-nonene. The product
distribution is strongly dependent on the catalyst used. In the
case of 2,7-tetradecene was obtained virtually selectively; in
contrast, the more active complex 1 gave 7-tetradecene in a
selectivity of only 63% at a high conversion. The by-product
obtained was essentially 6-tridecene from the cross-metathesis of
1-octene with 2-octene.
[0117] Ring-opening metathesis polymerization (ROMP) of
1,5-cyclooctadiene
[0118] ROMP of 1,5-cyclooctadiene. NMR comparison of a
ruthenium-dicarbene complex with a ruthenium-carbene phosphine
complex. (T=25.degree. C., 1.70 .mu.mol of catalyst in 0.55 ml of
CD.sub.2Cl.sub.2; [1,5-cyclooctadiene]/[catalyst]--250:1)
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[0119] The same applies to ROMP of cyclooctene: ROMP of
cyclooctadiene. NMR Kinetics of a ruthenium-dicarbene complex
compared to a ruthenium-carbene phosphine complex. (T=25.degree.
C.; 2.50 .mu.mol of catalyst in 0.50 ml of CD.sub.2Cl.sub.2;
[cyclooctadiene]/[catalyst]--250:1.
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