Heterocyclyl ligand containing ruthenium and osmium catalysts

Details Heterocyclyl ligand containing ruthenium and osmium catalysts Heterocyclyl ligand containing ruthenium and osmium catalysts

2000-05-26

2002-07-09

Wu, David W. (Department: 1713)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C502S162000, C502S156000, C502S155000, C526S161000, C526S171000, C526S172000, C556S013000, C556S136000

Reexamination Certificate

active

06417363

ABSTRACT:

The invention relates to novel penta- and hexa-coordinated, bridged ruthenium and osmium catalysts, to their preparation and to their use in the synthesis of polymers, in the ring-closure metathesis of diolefins, in the cross metathesis of olefins and in the isomerisation of olefins.
Thermal metathesis polymerisation of so-called strained cycloolefins, which has recently acquired great importance, requires suitable catalysts. Whereas, at first, systems consisting of catalyst and co-catalyst were used—see, for example, U.S. Pat. No. 4,060,468 and WO 93/13171—one-component catalysts have also been known for a relatively long time [Thoi, H. H., Ivin, K. J., Rooney, J. J.,
J. Mot. Catal
. 15:245-270 (1982)]. So-called “metal carbenes”, namely ruthenium and osmium complexes, having a ═CR*R** group bonded to the metal central atom, are especially suitable for that application [WO 93/20111; Kanaoka, S., Grubbs, R. H.,
Macromolecules
28:4707-4713 (1995); Fraser, C., Hillmyer, M., Gutierrez, E., Grubbs, R. H.,
Polym. Prepr
. 36:237-238 (1995); Schwab, P., France, M. B., Ziller, J. W., Grubbs, R. H.,
Angew. Chem
. 107:2179-2181 (1995)]. That type of complex is also suitable for catalysing ring-closure in dienes (WO 96104289 or WO 97/06185).
The known metal carbene catalysts are penta-coordinated and contain as neutral e donor ligands, in addition to the group ═CR*R**, identical tertiary phosphine groups bound to the central atom. The problem underlying the present invention is to prepare further, improved catalysts for the synthesis of polymers, for the ring-closure metathesis of olefins and for the isomerisation of olefins.
It has been found, surprisingly, that penta- and hexa-coordinated ruthenium and osmium complexes with a mono- or bi-cyclic, aromatic heterocyclyl group containing at least one nitrogen atom that is coordinated with the ruthenium or osmium central atom are excellent catalysts for metathesis reactions and the ring-closure of dienes. By suitable selection of the neutral ligands it is possible to control the reactivity, for example the latency, in a specific manner over a wide range.
The invention relates to compounds of formulae
wherein Me is ruthenium or osmium;
L
1
and L
2
are neutral ligands having electron donor properties;
X is an anionic ligand;
Y is oxygen or sulfur;
A is a direct bond, C
1
-C
4
alkylene or C
2
-C
4
alkylidene;
Z is a direct bond, oxygen, sulfur or the groups
wherein R
1
and R
2
are hydrogen or hydrocarbon radicals;
R is a hydrocarbon radical; and
Het-N is mono- or bi-cyclic, aromatic heterocyclyl having at least one nitrogen atom that is coordinated with Me;
and to isomers thereof.
The invention relates also to compounds of formulae Ia and Ib including all cases of isomerism, for example of the coordination isomerism or bond isomerism type, especially stereoisomers, that arise as a result of different spatial arrangement of the ligands about the central atom. Compounds of formula Ia include the following isomeric structures of formulae
wherein L
1
, X, Y, A, Z, R and Het-N are as defined hereinbefore.
The invention relates also to stereoisomeric compounds that arise as a result of the presence of a chiral centre in one of the mentioned ligands or in a side chain. Those cases of isomerism include optically pure enantiomers, diastereoisomers and also racemic mixtures.
The definitions and terms used in the context of the description of the present invention preferably have the following meanings:
The anionic ligand X is, for example, hydride (H
−
) or is derived from inorganic or organic acids and, by way of example, is selected from the group of the halides, for example fluoride, chloride or bromide, fluoro complexes of the type BF
4
−
, PF
6
−
, SbF
6
−
or AsF
6
−
, anions of oxy acids, for example carbonate, sulfate, phosphate, arsenate or antimonate, sulfonates, for example methanesulfonate, ethanesulfonate, n-propanesulfonate, n-butanesulfonate, trifluoromethanesulfonate (triflate), unsubstituted benzenesulfonate or p-toluenesulfonate, or benzenesulfonate or p-toluenesulfonate substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy or by halogen, especially fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxy-benzenesulfonate or pentafluorobenzenesulfonate, phosphonates, for example methyl phosphonate, ethyl phosphonate, propyl phosphonate, butyl phosphonate, phenyl phosphonate, p-methylphenyl phosphonate or benzyl phosphonate, carboxylates derived, for example, from a C
1
-C
8
carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenyl acetate, mono-, di- or tri-chloroacetate or trifluoroacetate, alcoholates, acetylides and anions of cyclopentadiene.
Further suitable anions are C
3
-C
18
—, preferably C
5
-C
14
— and especially C
5
-C
12
—, acetylides corresponding to the formula R
w
—C≡C
−
wherein 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 phenol or benzyl or phenol or benzyl mono- to tri-substituted by C
1
-C
4
alkyl or C
1
-C
4
alkoxy. Examples include isopropyl-, iso- and tert-butyl-, phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-, 2-isopropyl-, 2-isopropyl-6-methyl-, 2-tert-butyl-, 2,6-di-tert-butyl- and 2-methyl-6-tert-butylphenyl-acetylide.
Further suitable anionic ligands are also ligands that are derived from cyclopentadiene, for example cyclopentadienyl, and also indenyl, allyl, metallyl and crotyl.
Especially 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
−
, 4CH
3
-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
−
).
In the compounds of formulae Ia and Ib, the neutral ligand L
1
, and also the ligand L
2
denoting a neutral ligand, is tertiary phosphine having from 3 to about 40, preferably from 3 to 30, and especially from 3 to 18, carbon atoms. Preference is given to the tertiary phosphine of formula
wherein R
1
, R
2
and R
3
are, each independently of the others, C
1
-C
20
alkyl, C
4
-C
12
cycloalkyl, C
2
-C
11
heterocycloalkyl, C
6
-C
16
aryl, C
2
-C
15
heteroaryl or C
7
-C
16
aralkyl, wherein alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or aralkyl are unsubstituted or 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
6
aryl, —NO
2
, sulfo, ammonium and halogen; R
1
and R
2
together are tetra- or penta-methylene that is unsubstituted or substituted by C
1-C
6
alkyl, C
1
-C
6
haloalkyl, —NO
2
or by C
1
-C
6
alkoxy, or tetra- or penta-methylene that is condensed with one or two 1,2-phenylene and that is unsubstituted or substituted by C
1
-C
6
alkyl, C
1
-C
6
haloalkyl, —NO
2
or by C
1
-C
6
alkoxy, and R
3
is as defined above.
Examples of alkyl are methyl, ethyl, n- and iso-propyl and n-, sec- and tert-butyl, and also pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl and isomers thereof. An example of alkyl substituted by aryl is benzyl. Examples of alkoxy are methoxy, ethoxy, n- and isopropoxy and also n-, sec- and tert-butoxy. Examples of cycloalkyl are cyclo-butyl, -heptyl and -octyl and, especially, -pentyl and -hexyl.
Examples of aryl are phenyl and naphthyl. Examples of aryloxy are phenoxy and naphthyloxy. Aralkyl is preferably benzyl.
Examples of substituted cycloalkyl, aryl and aralkyl are cyclopentyl and cyclohexyl substituted by mono-, di- or tri-methyl or -methoxy or by mono-, bis- or tris-(trifluoromethyl), and also phenyl and benzyl substituted by those substituents.
Heterocycloalkyl preferably contains from one to four heteroatoms, the heteroatoms being selected from the group oxygen, sulfur and nitrogen. Examples of heterocycloalkyl include tetrahydrofuryl, pyrrolidinyl, piperazinyl and tetrahydrothienyl. Examples of

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