Highly active cationic ruthenium and osmium complexes for...

Details Highly active cationic ruthenium and osmium complexes for... Highly active cationic ruthenium and osmium complexes for...

2001-01-02

2003-07-08

Teskin, Fred (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S281000, C526S283000, C526S308000, C525S245000, C549S267000, C549S347000, C556S013000, C556S022000, C556S032000, C556S136000, C568S338000, C568S361000, C585S365000, C585S643000

Reexamination Certificate

active

06590048

ABSTRACT:

This application is a 371 of PCT/EP98/07364, filed on Nov. 17, 1998.
BACKGROUND OF THE INVENTION
The present invention describes the use of cationic vinylidene, allenylidene and higher cumulenylidene complexes of ruthenium or osmium as catalysts or catalyst precursors for olefin metathesis reactions of all types. The present invention also relates to new cationic allenylidene complexes of ruthenium and osmium which can be used as metathesis catalysts with preferred embodiment. These catalysts or catalyst precursors are easy to prepare from well accessible, stable and essentially non toxic starting materials, can be isolated and stored, they exhibit a high catalytic activity, a good compatibility with functional groups, solvents, water and additives, and they need not to be activated by any additive. Olefins of all types can be used as the substrates in the present invention.
PRIOR ART
Olefin metathesis refers to the interchange of carbon atoms between a pair of double bonds. Reactions of this type have found applications to processes of industrial importance (Reviews: Ivin, K. J.; Mol, J. C.
Olefin Metathesis
and
Metathesis Polymerization
, Academic Press, New York, 1997; Schuster, M. et al.,
Angew. Chem
. 1997, 109, 2125). Olefin metathesis reactions are catalyzed by various metal compounds. Many of the classical catalysts consist of mixtures of various components, they are ill defined in their chemical composition, show a poor compatibility with functional groups and are inefficient as a consequence of little active species present. More modern catalysts or catalyst precursors with a better application profile comprise complexes of the general types I-IX: (references: type I (M=Ru, Os): WO 96/04289, 15.02.1996; Nguyen S. T. et al.
J. Am. Chem. Soc
. 1992, 114, 3974; Nguyen S. T. et al.
J. Am. Chem. Soc
. 1993, 115, 9858; Schwab, P. et al.
Angew. Chem
. 1995, 107, 2179 (
Angew. Chem. Int. Ed. Engl
., 1995, 34, 2039); Schwab, P. et al.
J. Am. Chem. Soc
. 1996, 118, 100; Mohr, B. et al.
Organometallics
1996, 15, 4317; Wilhelm, T. E. et al.
Organometallics
1997, 16, 3867; Belderrain, T. R.
Organometallics
1997, 16, 4001. Type II (M=Mo, W): Schrock, R. R. et al.
J. Am. Chem. Soc
. 1990, 112, 3875; Fujimura, O. et al.
Organometallics
1996, 15, 1865. Type III: Quignard, F. et al.
J. Mol. Catal
. 1986, 36, 13. Type IV (M=Nb, Ta): Rocklage, S. M. et al.
J. Am. Chem. Soc
. 1981, 103, 1440; Wallace, K. C. et al.
Macromolecules
1987, 20, 448. Type V (cp=cyclopentadienyl or substituted cyclopentadienyl): U.S. Pat. No. 4,567,244, 28.01.1986. Type VI: Herrmann, W. A. et al.
Angew. Chem
. 1991, 103, 1704. Type VII: Nugent, W. A. et al.
J. Am. Chem. Soc
. 1995, 117, 8992. Type VII: Davie E. S.
J. Catal
. 1972, 24, 272. Type IX: Herrmann, W. A. et al.
Angew. Chem
. 1996, 108,1169.)
A major disadvantage of these complexes relates to their preparation which requires either reagents which are hazardous (e. g. type I: diazoalkanes), or difficult to prepare (e.g. type I: diphenylcyclopropene), or extremely sensitive (e. g. type II, III, IV, V, VI). Another disadvantage relates to the fact that some of these metathesis catalysts themselves are very sensitive to oxygen, moisture and/or polar functional groups and must be handled with great care under a strictly inert athmosphere (e. g. types II, III, IV, V). Another disadvantage relates to the fact that some of these complexes exhibit a reasonable reactivity only after activation with an additive, which can either be hazardous (e. g. for type IX: diazoalkanes) or toxic (e. g. for type VII: PbEt
4
). Catalysts of type VI are active only when deposited on special oxidic supports. Therefore a stringent need for metathesis catalysts persists, which reach or surpass the activity of the best catalysts I-IX described to date, but which are more readily accessible, require no hazardous reagents for their preparation, are robust, easy to isolate and handle, and need not be activated by any hazardous or toxic additives.
DETAILED DESCRIPTION OF THE INVENTION
The present invention, meets the criteria mentioned above. Surprisingly we find that cationic vinylidene, allenylidene and higher cumulenylidene complexes of ruthenium or osmium are highly efficient catalysts or catalyst precursors for olefin metathesis reactions of all types. These catalysts or catalyst precursors are easy to prepare from well accessible, stable and essentially non toxic starting materials, can be isolated and stored, they exhibit a high catalytic activity, a good compatibility with functional groups, solvents, water and additives, and they need not to be activated by any additive. Of the catalysts mentioned above, compounds of the general type XII, as specified below, are new compounds.
Specifically, the present invention relates to the use of vinylidene, allenylidene and higher cumulenylidene complexes of the general formula X as catalysts in olefin metathesis reactions of all types
wherein
M is Ru or Os;
X can be selected from any anionic ligand;
L
2
can be selected from any type of phosphine, sulfonated phosphine, fluorinated phosphine, functionalized phosphine bearing up to three aminoalkyl-, ammoniumalkyl-, alkoxyalkyl-, alkoxycarbonylalkyl-, hydroxycarbonylalkyl-, hydroxyalkyl-, ketoalkyl-groups, phosphite, phosphinite, phosphonite, arsine, stibene.
L
1
can be selected from any neutral &pgr;-bond ligand, preferably arene, substituted arene, heteroarene, independent of whether they are mono- or polycyclic;
A, B can be independently selected from hydrogen or a hydrocarbon from the group consisting of C1-C20 alkyl, aryl, C2-C20 alkenyl, alkynyl, C1-C20 alkoxy, carboxylate, carbamate, C2-C20 alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, C1-C20 alkylthio, alkylsulfonyl, alkylsulfinyl, arylthio, arylsulfonyl, arylsulfinyl, alkylamido, alkylamino, each of which may be substituted with C1-C10 alkyl, perfluoroalkyl, aryl, alkoxy or with halogen;
Y
−
may be selected from any non-coordinating anion;
n is 0-5;
in a preferred embodiment:
M is Ru or Os
X is halogen
L
2
is selected among phosphines bearing one or more secondary alkyl, tertiary alkyl, or cycloalkyl groups, preferably P(isopropyl)
3
, P(cyclohexyl)
3
, P(cyclopentyl)
3
, P(neopentyl)
3
, P(tertiobutyl)
3
.
L
1
is benzene or a substituted benzene derivative bearing up to six substituents which may be identical or not identical and can be independently selected from C1-C20 alkyl, aryl, alkoxy, aryloxy, alkylsulfonyl, arylsulfonyl, perfluoroalkyl, alkylthio, alkenylthio, C2-C10 alkenyl, alkynyl, alkenyloxy, alkynyloxy, or halogen, most preferably L
1
is toluene, xylene, cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetraline, naphthalene, or polycyclic arenes and their derivatives.
Y
−
is selected from PF
6
−
, BF
4
−
, BPh
4
−
, F
3
CSO
3
−
, H
3
CSO
3
−
, ClO
4
−
, SO
4
−
, NO
3
−
, PO
4
−
, CF
3
COO
−
, B(C
6
F
5
)
4
−
, RSO
3
−
, RCOO
−
with R being selected from C1-C20 alkyl, aryl
n is 1.
The most preferred catalysts of the present invention include XI
wherein
L
2
can be selected from P(isopropyl)
3
, P(cyclohexyl)
3
, P(cyclopentyl)
3
, P(neopentyl)
3
, P(tertiobutyl)
3
Y
−
is selected from PF
6
−
, BF
4
−
, BPh
4
−
, F
3
CSO
3
−
, H
3
CSO
3
−
, ClO
4
−
, SO
4
−
, NO
3
−
, PO
4
−
, CF
3
COO
−
, B(C
6
F
5
)
4
−
, RSO
3
−
, RCOO
−
with R being selected from C1-C20 alkyl, aryl
The preparation of these catalysts can be achieved by following the approach described in: Pilette, D. et al.,
Organometallics
1992, 11, 809.
The present invention also relates to new compounds of the general type XII
wherein
M is Ru or Os
X can be selected from any anionic ligand;
L
1
can be selected from any neutral &pgr;-bond ligand, preferably arene, substituted arene, heteroarene, independent of whether they are mono- or polycyclic;
L
2
is selected among phosphines, arsine or stibenes bear

Affiliated with

Also associated with

Rating

Highly active cationic ruthenium and osmium complexes for... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Highly active cationic ruthenium and osmium complexes for..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Highly active cationic ruthenium and osmium complexes for... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3049937