US 5,969,170 A · High activity ruthenium and osmium metal carbene complexes for olefin metathesis reactions

Abstract

Disclosed are ruthenium and osmium carbene compounds which are stable in the presence of a variety of functional groups and which can be used to catalyze olefin metathesis reactions on strained and unstrained cyclic and acyclic olefins. Specifically, the present invention relates to carbene compounds of the formula ##STR1## wherein: M is Os or Ru; R and R.sup.1 are independently selected from hydrogen and substituent groups C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.2 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl or C.sub.1 -C.sub.20 alkylsulfinyl; each substituent group optionally substituted with C.sub.1 -C.sub.5 alkyl, a halogen, C.sub.1 -C.sub.5 alkoxy or with a phenyl group optionally substituted with a halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are each trialkyl phosphine ligands where at least one of the alkyl groups on the phosphine is a secondary alkyl or a cycloalkyl. A broad array of metathesis reactions are enabled including ring-opening metathesis polymerization of cyclic olefins, ring closing metathesis of acyclic dienes, cross metathesis involving at least one acyclic or unstrained cyclic olefin, depolymerization of unsaturated polymers and synthesis of telechelic polymers.

Claims19

Dependent claims

A compound of the formula ##STR32## wherein:

M is Os or Ru;
R and R.sup.1 are independently selected from the group consisting of hydrogen and a substituent group selected from the group consisting of C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.2 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl and C.sub.1 -C.sub.20 alkylsulfinyl;
X and X.sup.1 are independently selected from any anionic ligand;
and
L and L.sup.1 are independently selected from PR.sup.3 R.sup.4 R.sup.5 wherein R.sup.3 is selected from the group consisting of neophyl, secondary alkyl and cycloalkyl and wherein R.sup.4 and R.sup.5 are independently selected from the group consisting of aryl, neophyl, C.sub.1 -C.sub.10 primary alkyl, secondary alkyl and cycloalkyl.

2 more elements

A compound of the formula ##STR33## wherein:

M is Os or Ru;
M is Os or Ru;
R and R.sup.1 are independently selected from the group consisting of hydrogen and a substituent group selected from the group consisting of vinyl, C.sub.1 -C.sub.10 alkyl, aryl, C.sub.1 -C.sub.10 carboxylate, C.sub.2 -C.sub.10 alkoxycarbonyl, C.sub.1 -C.sub.10 alkoxy, aryloxy;
each substituent group optionally substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, unsubstituted phenyl, or a substituted phenyl group substituted with halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy;
L and L.sup.1 are the same or different and are phosphines of the formnula PR.sup.3 R.sup.4 R.sup.5 wherein R.sup.3 is selected from the group consisting of neophyl, secondary alkyl and cycloalkyl and wherein R.sup.4 and R.sup.5 are independently selected from the group consisting of aryl, neophyl, C.sub.1 -C.sub.10 primary alkyl, secondary alkyl and cycloalkyl;
and
X and X.sup.1 are independently selected from the group consisting of halogen, hydrogen, diketonates, and a substituent group selected from the group consisting of C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 alkoxide, aryloxide, C.sub.2 -C.sub.20 alkoxycarbonyl, arylcarboxylate, C.sub.1 -C.sub.20 carboxylate, aryl or C.sub.1 -C.sub.20 alkylsulfonate, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl, C.sub.1 -C.sub.20 alkylsulfinyl, each substituent group optionally substituted with C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, unsubstituted phenyl or with a substituted phenyl group substituted with halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy.

4 more elements

Dependencies are inferred from the claim text.

High activity ruthenium and osmium metal carbene complexes for olefin metathesis reactions

Life of this patent

High activity ruthenium and osmium metal carbene complexes for olefin metathesis reactions

Life of this patent

Abstract

Claims19