Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization

Processes for the synthesis of several new carbene compounds of ruthenium and osmium are provided. These novel complexes function as stable, well-defined catalysts for the metathesis polymerization of cyclic olefins.

BACKGROUND OF THE INVENTION 
This invention relates to new ruthenium and osmium metal carbene complex 
compounds and their utility in an improved catalytic process for olefin 
metathesis polymerization. 
During the past two decades, research efforts have enabled an in depth 
understanding of the olefin metathesis reaction as catalyzed by early 
transition metal complexes. In contrast, the nature of the intermediates 
and the reaction mechanism for Group VIII transition metal catalysts has 
remained elusive. In particular, the oxidation states and ligation of the 
ruthenium and osmium metathesis intermediates are not known. Furthermore, 
the discrete ruthenium and osmium carbene complexes isolated to date do 
not exhibit metathesis activity. 
Many ruthenium and osmium metal carbenes have been reported in the 
literature (for example, see Burrell, A. K., Clark, G. R., Rickard, C. E. 
F., Roper, W. R., Wright, A. H., J. Chem. Soc., Dalton Trans., 1991, Issue 
1, pp. 609-614). 
SUMMARY OF THE INVENTION 
The present invention involves a reaction of a ruthenium or osmium compound 
with either a cyclopropene or a phosphorane to produce well-defined 
carbene compounds which can be called carbene complexes and which can 
catalyze the polymerization of cyclic olefin via ring-opening metathesis. 
The carbene compounds of the present invention are the only Ru and Os 
carbene complexes known to date in which the metal is formally in the +2 
oxidation state, has an electron count of 16, and is pentacoordinate. The 
compounds claimed herein are active catalysts for ring-opening metathesis 
polymerization ("ROMP"). Most metathesis catalysts presently known are 
poisoned by functional groups and are, therefore, incapable of catalyzing 
metathesis polymerization reactions in protic or aqueous solvent systems. 
Thus, the present invention pertains to compounds of the formula 
##STR1## 
wherein: 
M is Os or Ru; 
R and R.sup.1 are independently selected from hydrogen; C.sub.2 -C.sub.20 
alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 
-C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 
alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 
alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 
alkylsulfonyl or C.sub.1 -C.sub.20 alkylsulfinyl; each optionally 
substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy 
or with a phenyl group optionally substituted with halogen, C.sub.1 
-C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; 
X and X.sup.1 are independently selected from any anionic ligand; and 
L and L.sup.1 are independently selected from any neutral electron donor. 
In one embodiment of these compounds, they can be in the form wherein 2, 3, 
or 4 of the moieties X, X.sup.1, L, and L.sup.1 can be taken together to 
form a chelating multidentate ligand. In one aspect of this embodiment, X, 
L, and L.sup.1 can be taken together to form a cyclopentadienyl, indenyl, 
or fluorenyl moiety. 
The present invention also pertains to a method of preparing the 
aforementioned ruthenium and osmium compounds comprising reacting a 
compound of the formula (XX.sup.1 ML.sub.n L.sup.1.sub.m).sub.p, in the 
presence of solvent, with a cyclopropene of the formula 
##STR2## 
wherein: 
M, X, X.sup.1, L, and L.sup.1 have the same meaning as indicated above; 
n and m are independently 0-4, provided n+m=2, 3 or 4; 
p is an integer equal to or greater than 1; and 
R.sup.2 and R.sup.3 are independently selected from hydrogen; C.sub.1 
-C.sub.18 alkyl, C.sub.2 -C.sub.18 alkenyl, C.sub.2 -C.sub.18 alkynyl, 
C.sub.2 -C.sub.18 alkoxycarbonyl, aryl, C.sub.1 -C.sub.18 carboxylate, 
C.sub.1 -C.sub.18 alkenyloxy, C.sub.2 -C.sub.18 alkynyloxy, C.sub.1 
-C.sub.18 alkoxy, aryloxy, C.sub.1 -C.sub.18 alkylthio, C.sub.1 -C.sub.18 
alkylsulfonyl or C.sub.1 -C.sub.18 alkylsulfinyl; each optionally 
substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy 
or with a phenyl group optionally substituted with halogen, C.sub.1 
-C.sub.5 alkyl or C.sub.1-C.sub.5 alkoxy. 
In one embodiment of the process, X, L, and L.sup.1 are taken together to 
form a moiety selected from the group consisting of cyclopentadienyl, 
indenyl or fluorenyl, each optionally substituted with hydrogen; C.sub.2 
-C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, 
aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 
-C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 
-C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 
alkylsulfonyl, C.sub.1 -C.sub.20 alkylsulfinyl; each optionally 
substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy 
or with a phenyl group optionally substituted with halogen, C.sub.1 
-C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy. 
A still further method of preparing the compounds of this invention 
comprises reacting compound of the formula (XX.sup.1 ML.sub.n 
L.sup.1.sub.m).sub.p in the presence of solvent with phosphorane of the 
formula 
##STR3## 
wherein; 
M, X, X.sup.1, L, L.sup.1, n, m, p, R, and R.sup.1 have the same meaning as 
indicated above; and 
R.sup.4, R.sup.5 and R.sup.6 are independently selected from aryl, C.sub.1 
-C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy or phenoxy, each optionally 
substituted with halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, 
or with a phenyl group optionally substituted with halogen, C.sub.1 
-C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy. 
Another embodiment of the invention comprises preparing compounds of 
Formulae II and III 
##STR4## 
from compound of Formula I 
##STR5## 
comprising reacting said compound of Formula I, in the presence of 
solvent, with compound of the formula M.sup.1 Y wherein: 
M, R, R.sup.1 X, X.sup.1, L, and L.sup.1 have the same meaning as indicated 
above, and wherein: 
(1) M.sup.1 is Li, Na or K, and Y is C.sub.1 -C.sub.10 alkoxide or 
arylalkoxide each optionally substituted with C.sub.1 -C.sub.10 alkyl or 
halogen, diaryloxide; or 
(2) M.sup.1 is Na or Ag, and Y is ClO.sub.4, PF.sub.6, BF.sub.4, SbF.sub.6, 
halogen B(aryl).sub.4, C.sub.1 -C.sub.10 alkyl sulfonate or aryl 
sulfonate. 
Another embodiment of the present invention is a method of preparing 
compounds of structures of Formulae IV and V 
##STR6## 
from compound of Formula I 
##STR7## 
comprising reacting said compound I, in the presence of solvent, with 
L.sup.2 wherein: 
M, R, R.sup.1 X, and X.sup.1 have the same meaning as indicated above; and 
L, L.sup.1, and L.sup.2 are independently selected from any neutral 
electron donor. 
The compounds of Formulae II, III, IV, and V are species of, i.e., fall 
within, the scope of compounds of Formula I. In other words, certain 
compounds of Formula I are used to form by ligand exchange other compounds 
of Formula I. In this case, X and X.sup.1 in Formula I are other than the 
Y in Formulae II and III that replaces X. Similarly, L and L.sup.1 in 
Formula I are other than the L.sup.2 in Formulae IV and V. If any 2, 3, or 
4 of X, X.sup.1, L, and L.sup.1 form a multidentate ligand of Formula I, 
only the remaining ligand moieties would be available for ligand 
replacement. 
Still another embodiment of the present invention involves the use of 
compound I as a catalyst for polymerizing cyclic olefin. More 
specifically, this embodiment comprises metathesis polymerization of a 
polymerizable cyclic olefin in the presence of catalyst of the formula 
##STR8## 
in the presence of solvent, wherein: M, R, R.sup.1, X, X.sup.1, L and 
L.sup.1 have the same meaning as indicated above. 
The reference above to X, X.sup.1, L, and L.sup.1 having the same meaning 
as indicated above refers to these moieties individually and taken 
together to form a multidentate ligand as described above. 
DETAILED DESCRIPTION 
The ruthenium and osmium metal complexes of the present invention are 
useful as catalysts in ring-opening metathesis polymerization, 
particularly in the living polymerization of strained cyclic olefins. 
Although all the criteria for a living polymer have not been completely 
established, the term living is used in the sense that the propagating 
moiety is stable and will continue to polymerize additional aliquots of 
monomer for a period after the original amount of monomer has been 
consumed. Aspects of this invention include the metal complex compounds, 
methods for their preparation, as well as their use as catalysts in the 
ROMP reaction. Uses for the resultant polymer are well documented in the 
book, Olefin Metathesis, by K. J. Ivin, Academic Press, Harcourt Brace 
Jovanovich Publishers (1983). 
The intermediate compounds (XX.sup.1 ML.sub.n L.sup.1.sub.m).sub.p are 
either available Commercially or can be prepared by standard known 
methods. 
The phosphorane and cyclopropene reactants used in the present invention 
may be prepared in accordance with the following respective references. 
Schmidbaur, H. et al., Phosphorus and Sulfur, Vol. 18, pp. 167-170 (1983); 
Carter, F. L., Frampton, V. L., Chemical Reviews, Vol. 64, No. 5 (1964). 
In the compounds of Formula I: 
alkyl can include methyl, ethyl, n-propyl, i-propyl, or the several butyl, 
pentyl or hexyl isomers; 
alkenyl can include 1-propenyl, 2-propenyl; 3-propenyl and the different 
butenyl, pentenyl and hexenyl isomers, 1,3-hexadienyl and 
2,4,6-heptatrienyl, and cycloalkenyl; 
alkenyloxy can include H.sub.2 C.dbd.CHCH.sub.2 O, (CH.sub.3).sub.2 
C.dbd.CHCH.sub.2 O, (CH.sub.3)CH.dbd.CHCH.sub.2 O, 
(CH.sub.3)CH.dbd.C(CH.sub.3)CH.sub.2 O and CH.sub.2 .dbd.CHCH.sub.2 
CH.sub.2 O; 
alkynyl can include ethynyl, 1-propynyl, 3-propynyl and the several 
butynyl, pentynyl and hexynyl isomers, 2,7-octadiynyl and 
2,5,8-decatriynyl; 
alkynyloxy can include HC.tbd.CCH.sub.2 O, CH.sub.3 C.tbd.CCH.sub.2 O and 
CH.sub.3 C.tbd.CCH.sub.2 OCH.sub.2 O; 
alkylthio can include, methylthio, ethylthio, and the several propylthio, 
butylthio, pentylthio and hexylthio isomers; 
alkylsulfonyl can include CH.sub.3 SO.sub.2, CH.sub.3 CH.sub.2 SO.sub.2, 
CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2, (CH.sub.3).sub.2 CHSO.sub.2 and the 
different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers; 
alkylsulfinyl can include CH.sub.3 SO, CH.sub.3 CH.sub.2 SO, CH.sub.3 
CH.sub.2 CH.sub.2 SO, (CH.sub.3).sub.2 CHSO and the different 
butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers; 
carboxylate can include CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.2 CO.sub.2, 
C.sub.6 H.sub.5 CO.sub.2, (C.sub.6 H.sub.5)CH.sub.2 CO.sub.2 ; 
aryl can include phenyl, p-tolyl and p-fluorophenyl; 
alkoxide can include methoxide, t-butoxide, and phenoxide; 
diketonates can include acetylacetonate and 2,4-hexanedionate; 
sulfonate can include trifluoromethanesulfonate, tosylate, and mesylate; 
phosphine can include trimethylphosphine, triphenylphosphine, and 
methyldiphenylphosphine; 
phosphite can include trimethylphosphite, triphenylphosphite, and 
methyldiphenylphosphite; 
phosphinite can include triphenylphosphinite, and 
methyldiphenylphosphinite; 
arsine can include triphenylarsine and trimethylarsine; 
stibine can include triphenylstibine and trimethylstibine; 
amine can include trimethylamine, triethylamine and dimethylamine; 
ether can include (CH.sub.3).sub.3 CCH.sub.2 OCH.sub.2 CH.sub.3, THF, 
(CH.sub.3).sub.3 COC(CH.sub.3).sub.3, CH.sub.3 OCH.sub.2 CH.sub.2 
OCH.sub.3, and CH.sub.3 OC.sub.6 H.sub.5 ; 
thioether can include CH.sub.3 SCH.sub.3, C.sub.6 H.sub.5 SCH.sub.3, 
CH.sub.3 OCH.sub.2 CH.sub.2 SCH.sub.3, and tetrahydrothiophene; 
amide can include HC(.dbd.O)N(CH.sub.3).sub.2 and 
(CH.sub.3)C(.dbd.O)N(CH.sub.3).sub.2; 
sulfoxide can include CH.sub.3 S(.dbd.O)CH.sub.3, (C.sub.6 H.sub.5).sub.2 
SO; 
alkoxy can include methoxy, ethoxy, n-propyloxy, isopropyloxy and the 
different butoxy, pentoxy and hexyloxy isomers, cycloalkoxy can include 
cyclopentyloxy and cyclohexyloxy; 
cycloalkyl can include cyclopropyl, cyclobutyl, cyclopentyl, and 
cyclohexyl; and 
cycloalkenyl can include cyclopentenyl and cyclohexenyl. 
The term "halogen" or "halide", either alone or in compound words such as 
"haloalkyl", denotes fluorine, chlorine, bromine or iodine. 
Alkoxyalkyl can include CH.sub.3 OCH.sub.2, CH.sub.3 OCH.sub.2 CH.sub.2, 
CH.sub.3 CH.sub.2 OCH.sub.2, CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 
and CH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 ; and alkoxycarbonyl can include 
CH.sub.3 OC(.dbd.O), CH.sub.3 CH.sub.2 OC(.dbd.O), CH.sub.3 CH.sub.2 
CH.sub.2 OC(.dbd.O), (CH.sub.3).sub.2 CHOC(.dbd.O) and the different 
butoxy-, pentoxy- or hexyloxycarbonyl isomers. 
A neutral electron donor is any ligand which, when removed from a metal 
center in its closed shell electron configuration, has a neutral charge, 
i.e., is a Lewis base. 
An anionic ligand is any ligand which when removed from a metal center in 
its closed shell electron configuration has a negative charge. The 
critical feature of the carbene compounds of this invention is the 
presence of the ruthenium or osmium in the +2 oxidation state, an electron 
count of 16 and pentacoordination. A wide variety of ligand moieties X, 
X.sup.1, L, and L.sup.1 can be present and the carbene compound will still 
exhibit its catalytic activity. 
A preferred embodiment of the compounds of the present invention is: 
A compound of the invention of Formula I wherein: 
R and R.sup.1 are independently selected from hydrogen, vinyl, C.sub.1 
-C.sub.10 alkyl, aryl, C.sub.1 -C.sub.10 carboxylate, C.sub.2 -C.sub.10 
alkoxycarbonyl, C.sub.1 -C.sub.10 alkoxy, aryloxy, each optionally 
substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy 
or with a phenyl group optionally substituted with halogen, C.sub.1 
-C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; 
X and X.sup.1 are independently selected from halogen, hydrogen, or C.sub.1 
-C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 alkoxide, aryloxide, C.sub.2 
-C.sub.20 alkoxycarbonyl, arylcarboxylate, C.sub.1 -C.sub.20 carboxylate, 
aryl or C.sub.1 -C.sub.20 alkylsulfonate, C.sub.1 -C.sub.20 alkylthio, 
C.sub.1 -C.sub.20 alkylsulfonyl, C.sub.1 -C.sub.20 alkylsulfinyl, each 
optionally substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 
-C.sub.5 alkoxy or with a phenyl group optionally substituted with 
halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; and 
L and L.sup.1 are independently selected from phosphine, sulfonated 
phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, 
amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine or thioether. 
A more preferred embodiment of Formula I comprises: 
A compound of the invention wherein: 
R and R.sup.1 are independently selected from hydrogen; vinyl, C.sub.1 
-C.sub.5 alkyl, phenyl, C.sub.2 -C.sub.5 alkoxycarbonyl, C.sub.1 -C.sub.5 
carboxylate, C.sub.1 -C.sub.5 alkoxy, phenoxy; each optionally substituted 
with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy or a phenyl 
group optionally substituted with halogen, C.sub.1 -C.sub.5 alkyl or 
C.sub.1 -C.sub.5 alkoxy; 
X and X.sup.1 are independently selected from Cl, Br, H, or benzoate, 
C.sub.1 -C.sub.5 carboxylate, C.sub.1 -C.sub.5 alkyl, phenoxy, C.sub.1 
-C.sub.5 alkoxy, C.sub.1 -C.sub.5 alkylthio, aryl, and C.sub.1 -C.sub.5 
alkyl sulfonate; each optionally substituted with C.sub.1 -C.sub.5 alkyl 
or a phenyl group optionally substituted with halogen, C.sub.1 -C.sub.5 
alkyl or C.sub.1 -C.sub.5 alkoxy; 
L and L.sup.1 are independently selected from aryl or C.sub.1 -C.sub.10 
alkylphosphine, aryl- or C.sub.1 -C.sub.10 alkylsulfonated phosphine, 
aryl- or C.sub.1 -C.sub.10 alkylphosphinite, aryl- or C.sub.1 -C.sub.10 
alkylphosphonite, aryl- or C.sub.1 -C.sub.10 alkylphosphite, aryl- or 
C.sub.1 -C.sub.10 alkylarsine, aryl- or C.sub.1 -C.sub.10 alkylamine, 
pyridine, aryl- or C.sub.1 -C.sub.10 alkyl sulfoxide, aryl- or C.sub.1 
-C.sub.10 alkylether, or aryl- or C.sub.1 -C.sub.10 alkylamide, each 
optionally substituted with a phenyl group optionally substituted with 
halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy. 
A further preferred embodiment of Formula I comprises: 
A compound of the present invention wherein: 
R and R.sup.1 are independently vinyl, H, Me, Ph; 
X and X.sup.1 are independently Cl, CF.sub.3 CO.sub.2, CH.sub.3 CO.sub.2 
CFH.sub.2 CO.sub.2, (CH.sub.3).sub.3 CO, (CF.sub.3).sub.2 (CH.sub.3)CO, 
(CF.sub.3) (CH.sub.3).sub.2 CO, PhO, MeO, EtO, tosylate, mesylate, or 
trifluoromethanesulfonate; and 
L and L.sup.1 are independently PMe.sub.3, PPh.sub.3, P(p-Tol).sub.3, 
P(o-Tol).sub.3, PMePh.sub.2, PPhMe.sub.2, P(CF.sub.3).sub.3, P(p-FC.sub.6 
H.sub.4).sub.3, pyridine, P(p-CF.sub.3 C.sub.6 H.sub.4).sub.3, 
(p-F)pyridine, (p-CF.sub.3)pyridine, P(C.sub.6 H.sub.4 -SO.sub.3 Na).sub.3 
or P(CH.sub.2 C.sub.6 H.sub.4 -SO.sub.3 Na).sub.3. 
For any of the foregoing described preferred groups of compounds, any 2, 3, 
or 4 of X, X.sup.1, L, L.sup.1 can be taken together to form a chelating 
multidentate ligand. Examples of bidentate ligands include, but are not 
limited to, bisphosphines, dialkoxides, alkyldiketonates, and 
aryldiketonates. Specific examples include Ph.sub.2 PCH.sub.2 CH.sub.2 
PPh.sub.2, Ph.sub.2 AsCH.sub.2 CH.sub.2 AsPh.sub.2, Ph.sub.2 PCH.sub.2 
CH.sub.2 C(CF.sub.3)O--, binaphtholate dianions, pinacolate dianions, 
Me.sub.2 P(CH.sub.2).sub.2 PMe.sub.2 and --OC(CH.sub.3).sub.2 
(CH.sub.3).sub.2 CO--. Preferred bidentate ligands are Ph.sub.2 PCH.sub.2 
CH.sub.2 PPh.sub.2 and Me.sub.2 PCH.sub.2 CH.sub.2 PMe.sub.2. Tridentate 
ligands include, but are not limited to, (CH.sub.3).sub.2 NCH.sub.2 
CH.sub.2 P(Ph)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2. Other preferred 
tridentate ligands are those in which X, L, and L.sup.1 are taken together 
to be cyclopentadienyl, indenyl or fluorenyl, each optionally substituted 
with C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 
-C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 
alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, 
aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, 
C.sub.1 -C.sub.20 alkylsulfonyl, C.sub.1 -C.sub.20 alkylsulfinyl, each 
optionally substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 
-C.sub.5 alkoxy or with a phenyl group optionally substituted with 
halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy. More 
preferably in compounds of this type, X, L, and L.sup.1 are taken together 
to be cyclopentadienyl or indenyl, each optionally substituted with 
hydrogen; vinyl, C.sub.1 -C.sub.10 alkyl, aryl, C.sub.1 -C.sub.10 
carboxylate, C.sub.2 -C.sub.10 alkoxycarbonyl, C.sub.1 -C.sub.10 alkoxy, 
aryloxy, each optionally substituted with C.sub.1 -C.sub.5 alkyl, halogen, 
C.sub.1 -C.sub.5 alkoxy or with a phenyl group optionally substituted with 
halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy. Most 
preferably, X, L, and L.sup.1 are taken together to be cyclopentadienyl, 
optionally substituted with vinyl, hydrogen, Me or Ph. Tetradentate 
ligands include, but are not limited to O.sub.2 C(CH.sub.2).sub.2 P(Ph) 
(CH.sub.2).sub.2 P(Ph) (CH.sub.2).sub.2 CO.sub.2, phthalocyanines, and 
porphyrins. 
The most preferred carbene compounds of the present invention include: 
##STR9## 
The compounds of the present invention can be prepared in several different 
ways, each of which is described below. 
The most general method for preparing the compounds of this invention 
comprises reacting (XX.sup.1 ML.sub.n L.sup.1.sub.m).sub.p with a 
cyclopropene or phosphorane in the presence of a solvent to produce a 
carbene complex, as shown in the equations. 
##STR10## 
wherein: 
M, X, X.sup.1, L, L.sup.1, n, m, p, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and 
R.sup.6 are as defined above. Preferably, R.sup.2, R.sup.3, R.sup.4, 
R.sup.5, and R.sup.6 are independently selected from the group consisting 
of C.sub.1 -C.sub.6 alkyl or phenyl. 
Examples of solvents for this reaction include organic, protic, or aqueous 
solvents which are inert under the reaction conditions, such as: aromatic 
hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, 
alcohols, water, or mixtures thereof. Preferred solvents include benzene, 
toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, 
tetrahydrofuran, diethylether, pentane, methanol, ethanol, water, or 
mixtures thereof. More preferably, the solvent is benzene, toluene, 
p-xylene, methylene chloride, dichloroethane, dichlorobenzene, 
tetrahydrofuran, diethylether, pentane, methanol, ethanol, or mixtures 
thereof. 
A suitable temperature range is from about -20.degree. C. to about 
125.degree. C., preferably 35.degree. C. to 90.degree. C., and more 
preferably 50.degree. C. to 65.degree. C. Pressure is not critical but may 
depend on the boiling point of the solvent used, i.e., use sufficient 
pressure to maintain a solvent liquid phase. Reaction times are not 
critical, and can be from several minutes to 48 hours. The reactions are 
generally carried out in an inert atmosphere, most preferably nitrogen or 
argon. 
The reaction is usually carried out by dissolving the compound (XX.sup.1 
ML.sub.n L.sup.1.sub.m).sub.p, in a suitable solvent, adding the 
cyclopropene (preferably in a solvent) to a stirred solution of the 
compound, and optionally heating the mixture until the reaction is 
complete. The progress of the reaction can be monitored by any of several 
standard analytical techniques, such as infrared or nuclear magnetic 
resonance. Isolation of the product can be accomplished by standard 
procedures, such as evaporating the solvent, washing the solids (e.g., 
with alcohol or benzene), and then recrystallizing the desired carbene 
complex. Whether the moieties X, X.sup.1, L, or L.sup.1 are (unidentate) 
ligands or some taken together to form multidentate ligands will depend on 
the starting compound which simply carries these ligands over into the 
desired carbene complex. 
In one variation of this general procedure, the reaction is conducted in 
the presence of HgCl.sub.2, preferably 0.01 to 0.2 molar equivalents, more 
preferably 0.05 to 0.1 equivalents, based on XX.sup.1 ML.sub.n 
L.sup.1.sub.m. In this variation, the reaction temperature is preferably 
15.degree. C. to 65.degree. C. 
In a second variation of the general procedure, the reaction is conducted 
in the presence of ultraviolet radiation. In this variation, the reaction 
temperature is preferably -20.degree. C. to 30.degree. C. 
It is also possible to prepare carbene complexes of this invention by 
ligand exchange. For example, L and/or L.sup.1 can be replaced by a 
neutral electron donor, L.sup.2, in compounds of Formula I by reacting 
L.sup.2 with compounds of Formula I wherein L, L.sup.1, and L.sup.2 are 
independently selected from phosphine, sulfonated phosphine, phosphite, 
phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, 
carbonyl, nitrosyl, pyridine or thioether. Similarly, X and/or X.sup.1 can 
be replaced by an anionic ligand, Y, in compounds of Formula I by reacting 
M.sup.1 Y with compounds of Formula I, wherein X and X.sup.1 are 
independently selected from halogen, hydrogen, or C.sub.1 -C.sub.20 alkyl, 
aryl, C.sub.1 -C.sub.20 alkoxide, aryloxide, C.sub.2 -C.sub.20 
alkoxycarbonyl, arylcarboxylate, C.sub.1 -C.sub.20 carboxylate, aryl or 
C.sub.1 -C.sub.20 alkylsulfonate, C.sub.1 -C.sub.20 alkylthio, C.sub.1 
-C.sub.20 alkylsulfonyl, C.sub.1 -C.sub.20 alkylsulfinyl, each optionally 
substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy 
or with a phenyl group optinally substituted with halogen, C.sub.1 
-C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy. These ligand exchange reactions 
are typically carried out in a solvent which is inert under the reaction 
conditions. Examples of solvents include those described above for the 
preparation of the carbene complex. 
The compounds of this invention are useful as catalysts in the preparation 
of a wide variety of polymers which can be formed by ring-opening 
metathesis polymerization of cyclic olefins. Therefore, one embodiment of 
this invention is an improved polymerization process comprising metathesis 
polymerization of a cyclic olefin, wherein the improvement comprises 
conducting the polymerization in the presence of a catalytic amount of a 
compound of Formula I. The polymerization reaction is exemplified for 
norbornene in the following equation: 
##STR11## 
wherein n is the repeat unit of the polymeric chain. 
Examples of cyclic olefins for this polymerization process include 
norbornene, norbornadiene, cyclopentene, dicyclopentadiene, cycloheptene, 
cyclo-octene, 7-oxanorbornene, 7-oxanorbornadiene, and cyclododecene. 
The polymerization reaction is generally carried out in an inert atmosphere 
by dissolving a catalytic amount of a compound of Formula I in a solvent 
and adding the cyclic olefin, optionally dissolved in a solvent, to the 
catalyst solution. Preferably, the reaction is agitated (e.g., stirred). 
The progress of the reaction can be monitored by standard techniques, 
e.g., nuclear magnetic resonance spectroscopy. 
Examples of solvents for the polymerization reaction include organic, 
protic, or aqueous solvents which are inert under the polymerization 
conditions, such as: aromatic hydrocarbons, chlorinated hydrocarbons, 
ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. 
Preferred solvents include benzene, toluene, p-xylene, methylene chloride, 
dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentane, 
methanol, ethanol, water, or mixtures thereof. More preferably, the 
solvent is benzene, toluene, p-xylene, methylene chloride, dichloroethane, 
dichlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, 
ethanol, or mixtures thereof. Most preferably, the solvent is toluene or a 
mixture of benzene and methylene chloride. The solubility of the polymer 
formed in the polymerization reaction will depend on the choice of solvent 
and the molecular weight of the polymer obtained. 
Reaction temperatures can range from 0.degree. C. to 100.degree. C., and 
are preferably 25.degree. C. to 45.degree. C. The ratio of catalyst to 
olefin is not critical, and can range from 1:5 to 1:10,000, preferably 
1:10 to 1:1,000. 
Because the compounds of Formula I are stable in the presence of protic 
solvents, the polymerization reaction may also be conducted in the 
presence of a protic solvent. This is very unusual among metathesis 
catalysts and provides a distinct advantage for the process of this 
invention over the processes of the prior art. Other advantages of the 
polymerization process of this invention derive from the fact that the 
compounds of Formula I are well-defined, stable Ru or Os carbene complexes 
providing high catalytic activity. Using such compounds as catalysts 
allows control of the rate of initiation, extent of initiation, and the 
amount of catalyst. Also, the well-defined ligand environment of these 
complexes provides flexibility in modifying and fine-tuning their activity 
level, solubility, and stability. In addition, these modifications enable 
ease of recovery of catalyst. 
General Description of the Preparation of Compounds of this Invention from 
Cyclopropenes 
A 50 ml Schlenk flask equipped with a magnetic stirbar is charged with 
(MXX.sup.1 L.sub.n L.sup.1.sub.m).sub.p (0.1 mmol) inside a 
nitrogen-filled drybox. Methylene chloride (2 ml) is added to dissolve the 
complex followed by 25 ml of benzene to dilute the solution. One 
equivalent of a cyclopropene is then added to this solution. The reaction 
flask is then capped with a stopper, removed from the box, attached to a 
reflux condenser under argon and heated at 55.degree. C. The reaction is 
then monitored by NMR spectroscopy until all the reactants have been 
converted to product. At the end of the reaction, the solution is allowed 
to cool to room temperature under argon and then filtered into another 
Schlenk flask via a cannula filter. All solvent is then removed in vacuo 
to give a solid. This solid is then washed with a solvent in which the 
by-product will be soluble but the desired product will not. After the 
washing supernatant is removed, the resulting solid powder is dried in 
vacuo overnight. Further purification via crystallization can be performed 
if necessary. 
The abbreviations Me, Ph, and THF used herein refer to methyl, phenyl, and 
tetrahydrofuran, respectively. 
Representative compounds of the present invention which are prepared in 
accordance with the procedure described above are exemplified in Table I. 
TABLE I 
__________________________________________________________________________ 
##STR12## 
Compound Name M X X.sup.1 
L L.sup.1 
R R.sup.1 
__________________________________________________________________________ 
Dichloro-3,3-diphenylvinyl- 
Ru 
Cl Cl PPh.sub.3 
PPh.sub.3 
H CHCPH.sub.2 
carbene-bis(triphenylphos- 
phine)ruthenium(II) 
Dibromo-3,3-diphenylvinyl- 
Ru 
Br Br PPh.sub.3 
PPh.sub.3 
H CHCPh.sub.2 
carbene-bis(triphenylphos- 
phine)ruthenium(II) 
Dichloro-3,3-diphenylvinyl- 
Ru 
Cl Cl PPh.sub.2 Me 
PPh.sub.2 Me 
H CHCPh.sub.2 
carbene-bis(methyldiphenyl- 
phosphine)ruthenium(II) 
Dibromo-3,3-diphenylvinyl- 
Ru 
Br Br PPh.sub.2 Me 
PPh.sub.2 Me 
H CHCPH.sub.2 
carbene-bis(methyldiphenyl- 
phosphine)ruthenium(II) 
Dichloro-3-methyl-3- phenylvinylcarbene- bis(triphenylphosphine)- 
ruthenium(II) Ru 
Cl Cl PPh.sub.3 
PPh.sub.3 
H 
##STR13## 
Dibromo-3-methyl-3- phenylvinylcarbene- bis(triphenylphosphine)- ruthenium 
(II) Ru 
Br Br PPh.sub.3 
PPh.sub.3 
H 
##STR14## 
Dichloro-3,3-dimethyl- vinylcarbene-bis(triphenyl- phosphine)ruthenium(II) 
1 Ru 
Cl Cl PPh.sub.3 
PPh.sub.3 
H 
##STR15## 
Bis(acetato)-3,3-diphenyl- vinylcarbene-bis(triphenyl- phosphine)ruthenium 
(II) Ru 
##STR16## 
##STR17## 
PPh.sub.3 
PPh.sub.3 
H 
##STR18## 
Acetato-3,3-diphenyl- phosphine)ruthenium(II)- chloride 
Ru 
##STR19## 
Cl PPh.sub.3 
PPh.sub.3 
H 
##STR20## 
3,3-Diphenylvinylcarbene- bis(trifluoroacetato)bis- (triphenylphosphine)- 
uthenium(II) Ru 
##STR21## 
##STR22## 
PPh.sub.3 
PPh.sub.3 
H 
##STR23## 
3,3-Diphenylvinylcarbene- n.sup.2 -pinacol-bis(triphenyl- phosphine)ruthen 
ium(II) Ru 
##STR24## PPh.sub.3 
PPh.sub.3 
H 
##STR25## 
3,3-Diphenylvinylcarbene- bis(t-butoxy)bis-(tri- phenylphosphine 
ruthenium- (II) 
Ru 
Me.sub.3 CO 
Me.sub.3 CO 
PPh.sub.3 
PPh.sub.3 
H 
##STR26## 
3,3-Diphenylvinylcarbene- bis(2-trifluoromethyl-2- propoxy)-bis(triphenyl- 
phosphine)ruthenium(II) 
Ru 
##STR27## 
##STR28## 
PPh.sub.3 
PPh.sub.3 
H 
##STR29## 
__________________________________________________________________________ 
These are representative examples of the ruthenium complexes. Analogous 
complexes could be made with osmium.

EXAMPLE I 
Synthesis of 
##STR30## 
In a typical reaction, a 200 ml Schlenk flask equipped with a magnetic 
stirbar was charged with RuCl.sub.2 (PPh.sub.3).sub.4 (6.00 g, 4.91 mmol) 
inside a nitrogen-filled drybox. Methylene chloride (40 mL) was added to 
dissolve the complex followed by 100 mL of benzene to dilute the solution. 
3,3-Diphenylcyclopropene (954 mg, 1.01 equiv) was then added to the 
solution via pipette. The reaction flask was capped with a stopper, 
removed from the box, attached to a reflux condenser under argon and 
heated at 53.degree. C. for 11 h. After allowing the solution to cool to 
room temperature, all the solvent was removed in vacuo to give a dark 
yellow-brown solid. Benzene (10 mL) was added to the solid and subsequent 
swirling of the mixture broke the solid into a fine powder. Pentane (80 
mL) was then slowly added to the mixture via cannula while stirring 
vigorously. The mixture was stirred at room temperature for 1 h and 
allowed to settle before the supernatant was removed via cannula 
filtration. This washing procedure was repeated two more times to ensure 
the complete removal of all phosphine by-products. The resulting solid was 
then dried under vacuum overnight to afford 4.28 g (98%) of Compound 1 as 
a yellow powder with a slight green tint. .sup.1 H NMR (C.sub.6 D.sub.6): 
.delta. 17.94 (pseudo-quartet=two overlapping triplets, 1H, Ru=CH, 
J.sub.HH =10.2 Hz, J.sub.PH =9.7 Hz), 8.33 (d, 1H, CH.dbd.CPh.sub.2, 
J.sub.HH 10.2 Hz). .sup.31 P NMR (C.sub.6 D.sub.6): .delta. 28.2 (s). 
.sup.13 C NMR (CD.sub.2 Cl.sub.2): .delta. 288.9 (t, M=C, J.sub.cp =10.4 
Hz), 149.9 (t, CH.dbd.CPh.sub.2, J.sub.cp =11.58 Hz). 
The carbene complex which is the compound formed in the above example is 
stable in the presence of water or alcohol. 
EXAMPLE II 
Synthesis procedure for 
##STR31## 
A 50 ml Schlenk flask equipped with a magnetic stirbar was charged with 
OsCl.sub.2 (PPh.sub.3).sub.3 (100 mg, 0.095 mmol) inside a nitrogen-filled 
drybox. Methylene chloride (2 ml) was added to dissolve the complex 
followed by 25 ml of benzene to dilute the solution. 
3,3-diphenylcyclopropene (18.53 mg, 1.01 eq) was then added to the 
solution via pipet. The reaction flask was capped with a stopper, removed 
from the box, attached to a reflux condenser under argon and heated at 
55.degree. C. for 14 h. After allowing the solution to cool to room 
temperature, all the solvent was removed in vacuo to give a dark 
yellow-brown solid. Benzene (2 ml) was added to the solid and subsequent 
swirling of the mixture broke the solid into a fine powder. Pentane (30 
ml) was then slowly added to the mixture via cannula while stirring 
vigorously. The mixture was stirred at RT for 1 h and allowed to settle 
before the supernatant was removed via cannula filtration. This washing 
procedure was repeated two more times to ensure the complete removal of 
all phosphine by-products. The resulting solid was then dried under vacuum 
overnight to afford 74.7 mg of Compound 2 as a yellow powder (80%). .sup.1 
H NMR (C.sub.6 D.sub.6): .delta.19.89 (pseudo-quartet=two overlapping 
triplets, 1H, Os=CH, J.sub.HH =10.2 Hz), 8.23 (d, 1H, CH.dbd.CPh.sub.2, 
J.sub.HH =10.2 Hz). .sup.31 P NMR (C.sub.6 D.sub.6): .delta. 4.98 (s). 
EXAMPLE III 
Synthesis of 
##STR32## 
A 50 ml Schlenk flask equipped with a magnetic stirbar was charged with 
RuCl.sub.2 (PPh.sub.3).sub.2 (.dbd.CH--CH.dbd.CPPh.sub.2) (100 mg, 0.18 
mmol) inside a nitrogen-filled drybox. Methylene chloride (10 ml) was 
added to dissolve the complex. AgCF.sub.3 CO.sub.2 (24.9 mg., 1 eq) was 
weighed into a 10 ml round-bottom flask, dissolved with 3 ml of THF. Both 
flasks were then capped with rubber septa and removed from the box. The 
Schlenk flask was then put under an argon atmosphere and the AgCF.sub.3 
CO.sub.2 solution was added dropwise to this solution via a gas-tight 
syringe over a period of 5 min while stirring. At the end of the addition, 
there was a lot of precipitate in the reaction mixture and the solution 
turned into a fluorescent green color. The supernatant was transferred 
into another 50 ml Schlenk flask under argon atmosphere via the use of a 
cannula filter. Subsequent solvent removal under in vacuo and washing with 
pentane (10 ml) afforded a green solid powder, Compound 3. Yield=92.4 mg 
(85%). .sup.1 H NMR (2:2:1 CD.sub.2 Cl.sub.2 :C.sub.6 D.sub.6 
:THF-d.sub.8): .delta. 18.77 (dt, 1H, Ru=CH, J.sub.HH =11.2 Hz, J.sub.PH 
=8.6 Hz), 8.40 (d, 1H), CH.dbd.CPh.sub.2, J.sub.HH =11.2 Hz). .sup.31 P 
NMR (2:2:1 CD.sub.2 Cl.sub.2 :C.sub.6 D.sub.6 :THF-d.sub.8) .delta. 29.4. 
.sup.1 H NMR (2:2:1 CD.sub.2 Cl.sub.2 :C.sub.6 D.sub.6 :THF-d.sub.8): 
.delta. 18.77 (dt, 1H, Ru=CH, J.sub.HH =11.2 Hz, J.sub.PH =8.6 Hz), 8.40 
(d, 1H), CH.dbd.CPh.sub.2, J.sub.HH =11.2 Hz). .sup.31 P NMR (2:2:1 
CD.sub.2 Cl.sub.2 :C.sub.6 D.sub.6 :THF-d.sub.8) .delta. 29.4. .sup.19 F 
NMR (2:2:1 CD.sub.2 Cl.sub.2 :C.sub.6 D.sub.6 :THF-d.sub.8) .delta. 75.8. 
19 F NMR (2:2:1 CD.sub.2 Cl.sub.2 
EXAMPLE IV 
Synthesis of 
##STR33## 
A 50 ml Schlenk flask equipped with a magnetic stirbar was charged with 
RuCl.sub.2 (PPh.sub.3).sub.2 (.dbd.CH--CH.dbd.CPh.sub.2) (100 mg, 0.11 
mmol) inside a nitrogen-filled drybox. Methylene chloride (10 ml) was 
added to dissolve the complex. AgCF.sub.3 CO.sub.2 (49.8 mg, 2 eq) was 
weighed into a 10 ml round-bottom flask, dissolved with 4 ml of THF. Both 
flasks were then capped with rubber septa and removed from the box. The 
Schlenk flask was then put under an argon atmosphere and the AgCF.sub.3 
CO.sub.2 solution was added dropwise via a gas tight syringe over a period 
of 5 min to the solution of ruthenium compound while stirring. At the end 
of the addition, there was a lot of precipitate in the reaction mixture 
and the solution turned into a fluorescent lime green color. The 
supernatant was transferred into another 50 ml Schlenk flask under argon 
atmosphere with the use of a cannula filter. Subsequent solvent removal in 
vacuo and washing with pentane (10 ml) afforded a green powder, Compound 
4. Yield=102 mg (87%). .sup.1 H NMR (2:2:1 CD.sub.2 Cl.sub.2 :C.sub.6 
D.sub.6 :THF-d.sub.8): .delta. 19.23 (dt, slightly overlapping) Ru=CH, 
J.sub.HH =11.5 Hz, J.sub.PH =5.4 Hz), 8.07 (d, 1H), CH.dbd.CPH.sub.2, 
J.sub.HH =11.5 Hz). .sup.31 P NMR (2:2:1 CD.sub.2 Cl.sub.2 :C.sub.6 
D.sub.6 :THF-d.sub.8) .delta. 28.6. .sup.19 F NMR (2:2:1 CD.sub.2 Cl.sub.2 
:C.sub.6 D.sub.6 :THF-d.sub.8) .delta. 75.7. 
EXAMPLE V 
Synthesis of 
##STR34## 
The reaction between [Ru(C.sub.5 Me.sub.5)Cl].sub.4 and 
3,3-diphenylcyclopropene was done under a nitrogen atmosphere. [Ru(C.sub.5 
Me.sub.5)Cl].sub.4 (100 mg, 0.092 mmoL) was dissolved in 10 mL of 
tetrahydrofuran. To this solution was added 3,3-diphenylcyclopropene (350 
mg, 1.82 mmoL). The resulting solution was stirred at room temperature for 
1 h. Petroleum ether (10 mL) was then added to the reaction mixture. It 
was stirred for an additional 30 min, and then all volatile components 
were removed from the reaction mixture under vacuum. The crude product was 
extracted with diethyl ether; volatiles were removed from the filtrate 
under vacuum to afford a dark colored, oily solid. This was further 
extracted with petroleum ether; volatiles were removed from the filtrate 
under vacuum to afford a very dark red-brown oil. This was recrystallized 
from petroleum ether at -40.degree. C. to afford dark crystals. NMR 
spectra of which are consistent with the formulation [Ru(C.sub.5 Me.sub.5) 
(CHC.dbd.CPh.sub.2)Cl].sub.n (value of n as yet undertermined: e.g., the 
product could be a dimer). 
EXAMPLE VI 
Polymerization of Norbornene Using Compound of Example 1 
(PPh.sub.3).sub.2 Cl.sub.2 Ru.dbd.CH--CH.dbd.CPh.sub.2 catalyzed 
polymerized 
norbornene in a 1:8 mixture of CH.sub.2 Cl.sub.2 /C.sub.6 H.sub.6 at room 
temperature to yield polynorbornene. A new signal, attributed to H.alpha. 
of the propagating carbene, was observed by .sup.1 H NMR spectroscopy at 
17.79 ppm. Its identity and stability was confirmed by preparing a block 
polymer with 2,3-dideuteronorbornene and perprotionorbornene. When 
2,3-dideuteronorbornene was added to the propagating species, the new 
carbene signal vanished and then reappeared when perprotionorbornene was 
added for the third block. 
EXAMPLE VII 
Polymerization of Norbornene Using Compound of Example 5 
[Ru(C.sub.5 Me.sub.5) (CHC.dbd.CPh.sub.2)Cl (14 mg, 0.030 mmoL) was 
dissolved in 1 mL of perdeuterated toluene under a nitrogen atmosphere. To 
this was added norbornene (109 mg, 1.16 mmoL). The reaction mixture became 
viscous within minutes as the norbornene polymerized. After 20 hrs at room 
temperature a .sup.1 H NMR spectrum of the reaction mixture was recorded, 
which showed polynorbornene and unreacted norbornene monomer in a ratio of 
82:12.