US 5,849,851 A · Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes

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 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 functional 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 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, and depolymerization of unsaturated polymers.

Claims27

Dependent claims

A process for metathesis polymerization of a cyclic olefin, comprising contacting a functionalized or unfunctionalized cyclic olefin with a compound of the formula ##STR33## wherein:

M is selected from the group consisting of Os and 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.1 -C.sub.20 alkyl, C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkoxycarbonyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy and aryloxy;
the substituent group optionally substituted with a moiety selected from the group consisting of C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, and phenyl;
the phenyl optionally substituted with a moiety selected from the group consisting of halogen, C.sub.1 -C.sub.5 alkyl, and 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 independently selected from any phosphine of the formula 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.

4 more elements

A process for metathesis polymerization of a functionalized cyclic olefin comprising, contacting a functionalized cyclic olefin with a compound of the formula ##STR34## wherein:

the functionalized cyclic olefin includes a moiety selected from the group consisting of alcohol, thiol, ketone, aldehyde, ester, ether, amine, amide, nitro acid, carboxylic acid, disulfide, carbonate, carboalkoxy acid, isocyanate, carbodiimide, carboalkoxy, and halogen;
M is selected from the group consisting of Os and Ru;
R and R.sup.1 are independently selected from the group consisting of hydrogen and a first 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, and aryloxy;
the first substituent group optionally substituted with a group selected from the group consisting of C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, and phenyl;
the phenyl optionally substituted with a group selected from the group consisting of halogen, C.sub.1 -C.sub.5 alkyl, and C.sub.1 -C.sub.5 alkoxy;
X and X.sup.1 are independently selected from the group consisting of halogen, hydrogen, diketonates, and a second 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, arylsulfonate, C.sub.1 -C.sub.20 alkylsulfonate, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl, and C.sub.1 -C.sub.20 alkylsulfinyl;
the secend substituent group optionally substituted with a group selected from the group consisting of C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, and phenyl;
the phenyl optionally substituted with a group selected from the group consisting of halogen, C.sub.1 -C.sub.6 alkyl, and C.sub.1 -C.sub.5 alkoxy;
and,
L and L.sup.1 are independently selected from any phosphine of the formula 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 selected from the group consisting of aryl, neophyl, C.sub.1 -C.sub.10 primary alkyl, secondary alkyl, and cycloalkyl.

7 more elements

Dependencies are inferred from the claim text.

Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes

Life of this patent

Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes

Life of this patent

Abstract

Claims27