Ruthenium and osmium carbene catalysts

Details Ruthenium and osmium carbene catalysts Ruthenium and osmium carbene catalysts

1999-12-15

2002-06-18

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...

C556S013000, C556S136000, C526S308000

Reexamination Certificate

active

06407190

ABSTRACT:

The invention relates to penta- and hexacoordinated ruthenium and osmium carbene catalyst, 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. Thai et al.,
J. Mol. Catal
. 15:245-270 (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 93/201111; S. Kanaoke 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)]. This type of complex is also suitable for catalysing ring closure in dienes [WO 96/04289]. The known catalysts are pentacoordinated and in addition to the group ═CR′R″ contain two identical tertiary phosphine groups, attached to the metal atoms, as neutral e
−
donor ligands [WO 93/20111; WO 96/04289]. Z. Wu et al., J. Amer. Chem. Soc. 1995, 117, 5503-5511 disclose on page 5 the alkanethio-substituted ruthenium carbene complex (trifluoroacetate)
2
(PPh
3
)
2
Ru(CHSCH
2
Ph). However, it is also disclosed on page 5508, left column, last sentence, that this complex is inactive for catalyzing the ROMP (=Ring Opening Metathesis Polymerization) of bicyclo[3.2.0]hept-6-ene.
The present invention is based on the object of providing further. improved catalysts for thermal metathesis polymerization. It has surprisingly been found that pentacoordinated ruthenium and osmium catalysts having a group ═CR′R″ (R′=hydrogen and R″=arylthio) attached to the central metal atom, and hexacoordinated ruthenium and osmium catalysts having the group ═CR′R″ in which one of the radicals R′ or R″ is an organic radical which is attached via a nonmetallic heteroatom of the oxygen, sulfur or nitrogen type to the carbon atom of the carbene group, are excellent catalysts for metathesis reactions and for the ring closure of dienes. By an appropriate choice of neutral and anionic ligands it is possible to exercise close control over the reactivity, for example the latency, over a wide range.
The invention provides compounds of the formula
in which Me and Me′ independently of one another are ruthenium or osmium;
X X′, Y and Y′ independently of one another are anionic ligands or X and Y and X′ and Y′ in each case together are bisanionic ligands;
L
1
, L
2
, L
2′
, L
3
, L
3′
, L
5
and L
5′
independently of one another are monodentate, neutral e
−
donor ligands;
L
4
is a bidentate- or, together with two of the ligands L
1
, L
2
, L
2′
, L
3′
, L
5
and L
5′
, a tetradentate-neutral e
−
donor ligand;
Z is sulfur or the group
in which R′″ is hydrogen or a hydrocarbon radical;
Z
1
and Z
1′
independently of one another are oxygen, sulfur or the groups
and A′;
R is unsubstituted or substituted arts if Z is sulfur or is a hydrocarbon radical if Z is the groups A and A′; and
R′ and R″ are a hydrocarbon radical, or an isomer of this compound;
with the exception of compounds (Ib), wherein one of L
1
, L
2
and L
3
represents carbonyl.
The invention likewise provides compounds of the formulae Ia-Ie 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. For compounds of the formula Ia the following isomeric structures of the formulae
are possible, in which Me, X, Y, L
1
, L
2
, Z and R are as defined above. For compounds of the formulae Ib-Ie analogous isomeric structures are possible, which are likewise provided by the present invention. The invention likewise provides sterereoisomeric compounds which result from the presence of a centre of chirality in one of the specified ligands or in a side chain. These cases of isomerism include optically pure enantiomners, diastereomers and racemic mixtures.
The terms and definitions used in the description of the present invention preferably have the following meanings:
In the compounds of the formula Ia-Ie Me and Me′ are preferably ruthenium
The anionic ligands X, X′, Y and Y′ 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
−
, SbFd
6
−
or AsF
6
−
, anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadlene.
The anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonata, 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 p-ethoxyphenylsulfonate, 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, 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 p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methyl-phenylphosphonate 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
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
18
—, preferably C
5
-C
14
— and, with particular preference, C
5
-C
12
acetylides, which may be 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

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