Ruthenium and osmium catalysts

Details Ruthenium and osmium catalysts Ruthenium and osmium catalysts

1999-12-16

2001-10-23

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S172000, C526S281000, C526S283000, C526S308000, C556S022000, C556S136000, C556S137000, C502S155000

Reexamination Certificate

active

06306987

ABSTRACT:

The invention relates to ruthenium and osmium carbene catalysts, to their preparation and to their use for synthesizing polymers, for ring-closing metathesis of olefins and for isomerizing olefins.
The thermal metathesis polymerization of cycloolefins which, are under ring strain, which has acquired great importance in recent times, requires appropriate catalysts. Whereas initially use was made of catalyst and cocatalyst—see, for example U.S. Pat. No. 4,060,468 and International Patent Application WO 93/13171—one-component catalysts have also been disclosed [H. H. Thoi et al,
J. Mol. Catal.
15:245270 (1982)]. Catalysts of particular interest for the application are so-called metal carbenes, i.e. transition metal compounds, for example ruthenium and osmium complexes, having a group ═CR*R** attached to the central metal atom [WO 93/20111; S. Kanaoka et al.,
Macromolecules
28:4707-4713 (1995); C. Fraseret al,
Polym. Prepr.
36:237-238 (1995); P. Schwab et al.,
Angew. Chem.
107:2179-2181 (1995)]. This type of complex is also suitable for catalysing ring closure in dienes [WO 96104289]
The present invention is based on the object of providing further, improved catalysts for thermal metathesis polymerization.
It has surprisingly been found that ruthenium and osmium carbenes having e
−
donor ligands coordinated on the metal are excellent catalysts for metathesis reactions and for the ring closure of dienes. By an appropriate choice of these ligands it is possible to exercise close control over the reactivity, for example the latency, over a wide range. The bridged e
−
donor ligand is incorporated in the course of polymerization into the growing polymer and thereby removed from the metal centre, leading to an increased reactivity in comparison with catalysts already known.
The invention provides a compound of the formula
in which
Me is ruthenium or osmium;
X
1
and X
2
independently of one another are anionic ligands, or X
1
and x
2
together are a bis-anionic ligand;
Y is oxygen, sulfur or the groups —NR
7
— or —PR—, where R
7
is hydrogen or a substituent from the group C
1
-C
6
alkyl, C
6
-C
13
aralkyl, sulfonyl and —C(═O)R
s2
and R
s2
is hydrogen or a substituent from the group C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
3
-C
12
cycloalkyl, C
3
-C
12
cycloalkenyl,
C
2
-C
11
heterocycloalkyl, C
2
-C
11
heterocycloalkenyl, C
5
-C
12
aryl, C
1
-C
9
heteroaryl,
C
6
-C
14
aralkyl, C
2
-C
13
heteroaralkyl, C
6
-C
14
aralkenyl and C
3
-C
13
heteroaralkenyl;
n is 0 or 1;
L
1
is tertiary phosphine;
and L
2
is a neutral e
−
donor ligand which is coordinated to the metal atom and is attached via the bridge group C* to the carbon atom of the carbene group and to Y, and isomers of such compounds.
The invention likewise provides compounds of the formula I including all cases of isomerism of the type, for example, of coordination isomerism or bond isomerism, which results from differing spatial arrangement of the ligands around the central atom, but also stereoisomers.
In a particularly preferred embodiment of the invention Me is preferably ruthenium.
The terms and definitions used in the description of the present invention preferably have the following meanings:
The anionic ligands X
1
and X
2
are, for example, hydride ions (H
−
) or are derived from inorganic or organic acids, examples being halides, e.g. F
−
, Cl
−
, Br
−
or I
−
, fluoro complexes of the type BF
4
−
, PF
6
−
, SbF
6
−
or AsF
6
−
, anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadiene.
Anions of oxygen acids are, for example, sulfate, phosphate, perchiorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C
1
-C
8
carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C
1
-C
4
alkyl-, C
1
-C
4
alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or pethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate.
Such anions are, for example, anions of oxygen acids, examples being sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate or carbonate, sulfonates, for example methylsulfonate, ethyisulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C
1
-C
4
alkyl-, C
1
-C
4
alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate or benzylphosphonate, carboxylates derived from a C
1
-C
8
carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, and also C
1
-C
12
—, preferably C
1
-C
6
—and, with particular preference, C
1
-C
4
alcoholates, which in particular are branched, being for example of the formula R
x
R
y
R
z
C—O
−
in which R
x
is H or C
1
-C
10
alkyl, R
y
is C
1
-C
10
alkyl and R
z
is C
1
-C
10
alkyl or phenyl, and the sum of the carbon atoms of R
x
, R
y
and R
z
is at least 2, preferably at least 3 and up to 10.
Other suitable anions are C
3
-C
~
—, preferably C
5
-C
14
— and, with particular preference, C
5
-C
12
acetylides, which are of the formula R
w
—C≡C
−
in which R
w
is C
1
-C
16
alkyl, preferably &agr;-branched C
3
-C
12
alkyl, for example of the formula R
x
R
y
R
z
C—, or is unsubstituted or mono- to tri-C
1
-C
4
alkyl or —C
1
-C
4
alkoxy-substituted phenyl or benzyl. Some examples are i-propyl, i- and t-butyl, phenyl, benzyl, 2-methylphenyl, 2,6-dimethylphenyl, 2-i-propylphenyl, 2-i-propyl-6-methylphenyl, 2-t-butylphenyl, 2,6-di-t-butylphenyl and 2-methyl-6-t-butylphenyl acetylide.
Further anionic ligands are organic radicals having negative charges, such as C
1
-C
12
alkyl, e.g. methyl, or aralkyl, e.g. benzyl
Particularly preferred anionic ligands X
1
and X
2
are H
−
, F
−
, Cl
−
, Br
−
, BF
4
−
, PF
6
−
, SbF
6
−
, AsF
6
−
, CF
3
SO
3
−
, C
6
H
5
—O
3
−
, 4-methyl-C
6
H
4
—SO
3
−
, 3,5-dimethyl-C
6
H
3
—SO
3
−
, 2,4,6-trimethyl-C
6
H
2
—SO
3
−
and 4-CF
3
13
C
6
H
4
—SO
3
−
and also cyclopentadienyl (Cp
−
). Cl
−
is particularly preferred.
Examples of bisanionic ligands X, X′, Y and Y′ are the bisanions of diols, diamines and hydroxyamines, such as catechol, N,N′-dimethyl-1,2-benzenediamine, 2-(methyl-amino)phenol, 3-(methylamino)-2-butanol and N,N′-bis(1,1-dimethylethyl)-1,2-ethanediamine.
Tertiary-substituted phosphine L
1
contains 3-about 40, preferably 3-30 and, with particular preference, 3-18 carbon atoms. The tertiary-substituted phosphine is preferably a compound of the formula
in which R
1
, R
2
and R
3
independently of one another are C
1
-C
20
alkyl, C
3
-C
12
cycloalkyl, C
2
-C
11
heterocycloalkyl, C
5
-C
12
aryl, C
1
-C
12
heteroaryl or C
6
-C
14
aralkyl, where alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and aralkyl are unsubstituted or substituted by one or more substituents of the group consisting of C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
haloalkyl, C
5
-C
12
aryl, —NO
2
, SO
3
−
, ammonium and halogen; the radicals R
1
and R
2
together are unsubstituted or C
1
-C
6
alkyl-, C
1
-C
6
haloalkyl-, —NO
2
— or C
1
-C
6
alkoxy-substituted tetra- or pentamethylene, which may be fused to 1 or 2 1,2-phenylene radicals, and R
3
is as defined above.
Examples of alkyl are methyl, ethyl and the isomers of propyl, butyl, pentyl, hexy

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