Ruthenium and osmium carbene carbonyl catalysts

Details Ruthenium and osmium carbene carbonyl catalysts Ruthenium and osmium carbene carbonyl catalysts

2000-09-25

2002-10-15

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C502S435000, C556S136000, C526S171000, C526S172000, C522S066000

Reexamination Certificate

active

06465554

ABSTRACT:

The invention relates to compositions of hexacoordinated ruthenium and osmium carbene carbonyl catalysts and to their use for the photoinduced synthesis of polymers, to novel coordinated ruthenium and osmium carbene carbonyl catalysts, and to processes for their preparation.
The metathesis polymerization of cycloolefins (ROMP: Ring Opening Metathesis Polymerization) which are under ring strain, which has acquired great importance in recent times, requires appropriate catalysts. Catalysts of particular interest for the application are so-called metal carbenes, i.e. transition metal compounds—ruthenium and osmium compounds, for example—having a group=CR′R″ attached to the metal atoms [WO 93/20111; S. Kanaoka et al.,
Macromolecules
28: 4707-4713 (1995); C. Fraser et al.,
Polym. Prepr.
36:237-238 (1995); P. Schwab et al.,
Angew. Chem.
107: 2179-2181 (1995)]. Suitable catalysts for photoinduced ROMP are described in WO 95/07310 and WO96/16103. Their applicability is limited by their cationic nature or low reactivity.
M. A. Esteruelas et al. in
Organometallics,
Vol. 13: 4258-4265 (1994) describe some hexacoordinated ruthenium and osmium carbenes of the formula
in which one of the radicals R
a
and R
b
is hydrogen and the other is phenyl or both are phenyl, but do not indicate the possibility of their use for ROMP.
It has surprisingly been found that hexacoordinated ruthenium and osmium carbenes having a carbonyl group as ligand and a vinyl group as substituent on the carbene group are excellent catalysts for photoinduced ring-opening metathesis. Through an appropriate choice of neutral ligands it is possible to exercise close control over the reactivity, for example the latency, over a wide range.
The invention provides compositions comprising
(&agr;) a cycloolefin or a mixture of cycloolefins; and
(&bgr;) a catalytic amount of at least one compound
in which
Me is ruthenium or osmium;
X and Y independently of one another are anionic ligands or together are a bis-anionic ligand;
L
1
and L
2
independently of one another are neutral ligands having electron donor properties and R
a
and R
b
independently of one another are hydrogen or hydrocarbon radicals,
and isomers of these compounds.
One particular embodiment provides compounds (I) in which Me is ruthenium, and also provides for their use.
Compounds (I) have the advantage that cyclic olefins, such as dicyclopentadiene (DCPD), can be polymerized in a photoinduced metathesis polymerization using a one-component catalyst. It has also been found that the polymerization takes place even in the presence of polymer additives, such as fillers, and that mouldings, films or coatings having excellent physical and mechanical properties are obtained. It has been observed, further, that the compositions comprising cyclic olefin and the compounds of the invention are stable to air and moisture and therefore exhibit great stability on storage. No particular protective measures are necessary for the polymerization, which offers considerable advantages in processing. It has also been found that, using these catalysts, DCPD can be copolymerized with other strained cycloolefin comonomers. This makes it possible to carry out controlled modification of properties and to adapt them to the desired end use.
The designations used in describing the present invention are defined as follows:
Suitable anionic ligands X and Y are, for example, the hydride ion (H
−
) or are ligands derived, for example, from organic or inorganic acids by elimination of protons, an example being halide (F
−
, Cl
−
, Br
−
and I
−
) or anions of oxygen acids or derivatives thereof, e.g. SnCl
6
2−
, BF
4
−
, PF
6
−
, SbF
6
−
or AsF
6
−
.
Anions of oxygen acids are, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C
1
-C
8
carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example mesylate, ethanesulfonate, propanesulfonate, n-butanesulfonate, trifluoromethanesulfonate (triflate), unsubstituted or C
1
-C
4
alkyl-, C
1
-C
4
alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted benzenesulfonate, for example tosylate, p-ethoxybenzenesulfonate, pentafluoro-benzenesulfonate or 2,4,6-triisopropylbenzenesulfonate.
Further anionic ligands are organic radicals which carry negative charges, examples being C
1
-C
12
alcoholates, especially C
1
-C
4
alcoholates, C
5
-C
12
acetylides or C
4
-C
8
cycloalkenyl radicals, e.g. cyclopentadienyl.
Particularly preferred anionic ligands are H
−
, F
−
, Cl
−
, Br
−
, BF
4
−
, PF
6
−
, SbF
6
−
, AsF
6
−
, CF
3
SO
3
−
, C
6
H
5
—SO
3
−
, 4-methyl-C
6
H
5
—SO
3
−
, 3,5-dimethyl-C
6
H
5
—SO
3
−
, 2,4,6-trimethyl-C
6
H
5
—SO
3
−
and 4-CF
3
—C
6
H
5
—SO
3
−
, and also cyclopentadienyl (Cp
−
). Cl
−
is particularly preferred.
Examples of bis-anionic ligands are the bisanions of diols, diamines and hydroxy amines, such as catechol, N,N′-dimethyl-1,2-benzenediamine, 2-(methylamino)phenol, 3-(methylamino)-2-butanol and N,N′-bis(1,1-dimethylethyl)-1,2-ethanediamine.
Neutral ligands L
1
, and L
2
are primarily tertiary phosphines having 3 to 40, especially 3 to 30 and, with particular preference, 3 to 18 carbon atoms. They are preferably of the formula:
PR
1
R
2
R
3
  (II),
in which R
1
, R
2
and R
3
independently of one another are C
1
-C
20
alkyl, C
4
-C
12
cycloalkyl, C
2
-C
11
heterocycloalkyl, C
6
-C
16
aryl, C
2
-C
16
heteroaryl or C
7
-C,
16
aralkyl, which may be substituted by one or more substituents selected from the group consisting of C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
haloalkyl, C
6
-C
16
aryl, —NO
2
, —SO
3
−
, ammonium and halogen; or the radicals R
1
and R
2
together are tetra- or pentamethylene which may be substituted by one or more substituents from the group consisting of C
1
-C
6
alkyl, C
1
-C
6
haloalkyl, —NO
2
and C
1
-C
6
alkoxy and may be fused to 1 or 2 bivalent 1,2-phenylene radicals, and R
3
is as defined above.
Examples of alkyl are methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. An example of aryl-substituted alkyl is benzyl. Examples of alkoxy are methoxy, ethoxy and the isomers of propoxy and butoxy.
Some examples of cycloalkyl are cyclobutyl, cycloheptyl or cyclooctyl and, in particular, cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl -,trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tris-trifluoromethyl-substituted cyclopentyl and cyclohexyl.
Examples of aryl are phenyl and naphthyl. Examples of aryloxy are phenoxy and naphthyloxy. Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluoromethyl-substituted phenyl. An example of aralkyl is benzyl. Examples of substituted aralkyl are methyl-,dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl -, bistrifluoromethyl-and tristrifluoromethyl-substituted benzyl.
Heterocycloalkyl has preferably one or two heteroatoms and heteroaryl one to four heteroatoms, the heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen. Some examples of heterocycloalkyl are tetrahydrofuryl, pyrrolidinyl, piperazinyl and tetrahydrothienyl. Some examples of heteroaryl are furyl, thienyl, pyrrolyl, pyridyl and pyrimidinyl.
Preference is given to compounds (I), and their use, in which L
1
and L
2
independently of one another are tertiary phosphine of the formula II in which R
1
, R
2
and R
3
are identical. Particular preference is given, furthermore, to radicals R
1
, R
2
and R
3
which are sterically bulky, such as cyclic or branched alkyl groups, especially &agr;,&agr;-dibranched alkyl groups

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