Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand

Patent metadata

Field	Value
Publication number	US-9238709-B2
Application number	US-201414497387-A
Country	US
Kind code	B2
Filing date	Sep 26, 2014
Priority date	Mar 29, 2004
Publication date	Jan 19, 2016
Grant date	Jan 19, 2016

Abstract

The invention provides novel organometallic complexes useful as olefin metathesis catalysts. The complexes have an N-heterocyclic carbene ligand and a chelating carbene ligand associated with a Group 8 transition metal center. The molecular structure of the complexes can be altered so as to provide a substantial latency period. The complexes are particularly useful in catalyzing ring closing metathesis of acyclic olefins and ring opening metathesis polymerization of cyclic olefins.

First claim

We claim:

1. A method for catalyzing an olefin metathesis reaction, comprising contacting an olefinic reactant with a complex having the structure of formula (I)

wherein:
α and β represent single bonds or unsaturated bonds, with the proviso that α and β cannot both be unsaturated bonds;
M is a Group 8 transition metal;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
Q is an organic diradical;
X 1 and X 2 are anionic ligands, and may be the same or different;
L 1 is a neutral electron donor ligand, and p is zero or 1;
when α is a single bond, L 2 is selected from NR 7 R 8 , PR 7 R 8 , N═CR 7 R 8 , and R 7 C═NR 8 , where R 7 and R 8 are independently selected from substituted and/or heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, and C 5 -C 24 aryl, or R 7 and R 8 can be taken together to form a heterocyclic ring;
when α is an unsaturated bond, L 2 is selected from NR′ and PR 7 , where R 7 is as defined previously, or L 2 and Z represent adjacent atoms in an aromatic ring;
Y and Z are linkages independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, —O—, —S—, —NR 9 , and —PR 9 —, wherein R 9 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, and further wherein Y and Z may represent adjacent atoms in an aromatic ring;
m is zero or 1;
n is zero or 1; and wherein
L 2 and the ligand containing Q are bonded to M in a trans orientation, and wherein the olefinic reactant and the complex having the structure of formula (I) are contacted under reaction conditions selected to enable olefin metathesis; and wherein the complex having the structure of formula (I) exhibits a latency period when contacted with the olefinic reactant.

2. The method for catalyzing an olefin metathesis reaction according to claim 1 , wherein the complex has the structure of formula (II)

wherein:
β represents a single bond or an unsaturated bond;
M is a Group 8 transition metal;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
Q is an organic diradical;
X 1 and X 2 are anionic ligands, and may be the same or different;
L 1 is a neutral electron donor ligand, and p is zero or 1;
R 7 and R 8 are independently selected from substituted and/or heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, and C 5 -C 24 aryl, or R 7 and R 8 can be taken together to form a heterocyclic ring;
Y and Z are linkages independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, —O—, —S—, —NR 9 , and —PR 9 —, wherein R 9 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, and further wherein Y and Z may represent adjacent atoms in an aromatic ring; and
wherein NR 7 R 8 and the ligand containing Q are bonded to M in a trans orientation.

3. The method for catalyzing an olefin metathesis reaction according to claim 2 , wherein R 7 and R 8 of the complex having the structure of formula (II) are C 1 -C 12 alkyl or C 5 -C 12 aryl, and Y is a substituted or unsubstituted methylene or ethylene linkage.

4. The method for catalyzing an olefin metathesis reaction according to claim 1 , wherein the complex has the structure of formula (III)

wherein:
β represents a single bond or an unsaturated bond;
M is a Group 8 transition metal;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
Q is an organic diradical;
X 1 and X 2 are anionic ligands, and may be the same or different;
L 1 is a neutral electron donor ligand, and p is zero or 1;
R 7 and R 8 are independently selected from substituted and/or heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, and C 5 -C 24 aryl, or R 7 and R 8 can be taken together to form a heterocyclic ring;
Y and Z are linkages independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, —O—, —S—, —NR 9 , and —PR 9 —, wherein R 9 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, and further wherein Y and Z may represent adjacent atoms in an aromatic ring; and
wherein PR 7 R 8 and the ligand containing Q are bonded to M in a trans orientation.

5. The method for catalyzing an olefin metathesis reaction according to claim 4 , wherein R 7 and R 8 of the complex having the structure of formula (III) are C 1 -C 12 alkyl or C 5 -C 12 aryl, and Y is a substituted or unsubstituted methylene or ethylene linkage.

6. The method for catalyzing an olefin metathesis reaction according to claim 5 , wherein R 7 and R 8 of the complex having the structure of formula (III) are phenyl and Y is ethylene.

7. The method for catalyzing an olefin metathesis reaction according to claim 1 , wherein the complex has the structure of formula (IV)

wherein:
M is a Group 8 transition metal;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
Q is an organic diradical;
X 1 and X 2 are anionic ligands, and may be the same or different;
L 1 is a neutral electron donor ligand, and p is zero or 1;
Y is a linkage selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, —O—, —S—, —NR 9 , and —PR 9 —, wherein R 9 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl; and wherein
the complex has a pyridine ligand,
wherein the pyridine ligand and the ligand containing Q are bonded to M in a trans orientation.

8. The method for catalyzing an olefin metathesis reaction according to claim 1 , wherein the complex has the structure of formula (V)

wherein:
M is a Group 8 transition metal;
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
Q is an organic diradical;
X 1 and X 2 are anionic ligands, and may be the same or different;
L 1 is a neutral electron donor ligand, and p is zero or 1; and
R 7 is selected from substituted and/or heteroatom-containing C

Assignees

• Materia Inc
• California Inst Of Techn

Inventors

• Ung Thay
• Schrodi Yann
• Trimmer Mark S
• Hejl Andrew
• Sanders Daniel
• Grubbs Robert H

Classifications

• C07D493/10

  Spiro-condensed systems · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C07C67/333

  by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) · CPC title

• C08G2261/11

  Homopolymers · CPC title

• C08G61/02 Primary

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title