# US 10,501,488 B2 · Metal carbene olefin metathesis catalysts

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- Number: US 10,501,488 B2
- Document ID: US10501488B2
- Status: Granted
- Kind: B2
- Application number: 15/762,918
- Filed: 2016-09-23
- Published: 2018-09-20
- Granted: 2019-12-10
- Earliest claimed: 2015-09-24
- Assignees: Umicore AG & Co. KG
- Applicants: Umicore AG & Co. KG
- Inventors: Michael A. Giardello; Mark S. Trimmer; Li-Sheng Wang; Noah H. Duffy; Adam M. Johns; Nicholas J. Rodak; Bryan A. Fiamengo; John H. Phillips
- Web page: https://patentgrep.com/patent/US10501488B2

## CPC

- C07F 15/0046: {Ruthenium compounds}
- C08G 61/08: of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
- C08L 65/00: Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers
- C08G 2261/3324: derived from norbornene
- C08G 2261/3325: derived from other polycyclic systems
- C08G 2261/418: Ring opening metathesis polymerisation [ROMP]
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

This invention relates generally to metal carbene olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry.

## Claims

### Claim 1

A metal carbene olefin metathesis catalyst represented by the structure of Formula (V):
wherein
Q is a two-atom linkage having the structure —CR11R12—CR13R14— or —CR11═CR13—, wherein R11, R12, R13, and R14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or functional groups;
R3 and R4 is unsubstituted phenyl or phenyl substituted with one or more substituents selected from the group consisting of C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide;
X1 and X2 are independently halogen; and are bonded to Ru in a trans orientation;
L2 is represented by Formula (1) or Formula (2):
wherein: R1p, R2p, R3p are each independently substituted or unsubstituted C6-C10 aryl, or substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl,
wherein: R8p, R9p, R10p are each independently substituted or unsubstituted C6-C10 aryl, or substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl,
m is 0, 1, or 2;
R1 and R2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or R1 and R2 may be linked together to form a ring that may be substituted or unsubstituted; and with the proviso that the catalyst of Formula (V) is not of structure:

### Claim 2 (depends on 1)

The metal carbene olefin metathesis catalyst according to claim 1, wherein:
m is 0;
Q is a two-atom linkage having the structure —CR11R12—CR13R14—, wherein R11, R12, R13, and R14 are each hydrogen;
R3 and R4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl;
X1 and X2 are Cl;
R1 is hydrogen, R2 is phenyl, vinyl, optionally substituted with one or more moieties selected from C1-C6 alkyl, or C1-C6 alkoxy; or R1 and R2 may be linked together to form a phenylindenylidene.

### Claim 3 (depends on 2)

The metal carbene olefin metathesis catalyst according to claim 2, wherein:
L2 is represented by Formula (1):
wherein: R1p, R2p, R3p are each independently substituted or unsubstituted C6-C10 aryl, or substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl.

### Claim 4 (depends on 3)

The metal carbene olefin metathesis catalyst according to claim 3, wherein:
R1p is selected from the group consisting of methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl and phenyl; and R2p and R3p are each phenyl.

### Claim 5 (depends on 4)

The metal carbene olefin metathesis catalyst according to claim 4, wherein the catalyst is selected from the group consisting of:

### Claim 6 (depends on 1)

The metal carbene olefin metathesis catalyst according to claim 1, wherein:
m is 0;
Q is a two-atom linkage having the structure —CR11R12—CR13R14—, wherein R11, R12, R13, and R14 are independently hydrogen;
R3 and R4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl;
X1 and X2 are Cl;
R1 is hydrogen, R2 is phenyl, vinyl, optionally substituted with one or more moieties selected from C1-C6 alkyl, or C1-C6 alkoxy; or R1 and R2 may be linked together to form a phenylindenylidene.

### Claim 7 (depends on 6)

The metal carbene olefin metathesis catalyst according to claim 6, wherein:
L2 is represented by Formula (2):
wherein: R8p, R9p, R10p are each independently substituted or unsubstituted C6-C10 aryl, or substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl.

### Claim 8 (depends on 7)

The metal carbene olefin metathesis catalyst according to claim 7, wherein: R8p and R9p are each independently selected from methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; and R10p is phenyl.

### Claim 9 (depends on 8)

The metal carbene olefin metathesis catalyst according to claim 8, wherein the catalyst is selected from the group consisting of:

### Claim 10

A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin and wherein the at least one metal carbene olefin metathesis catalyst is selected from the group consisting of:

### Claim 11 (depends on 10)

The ROMP composition according to claim 10, wherein the at least one cyclic olefin is a norbornene derivative.

### Claim 12 (depends on 1)

A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 1, wherein the resin composition comprises at least one cyclic olefin.

### Claim 13 (depends on 12)

The ROMP composition according to claim 12, wherein the at least one cyclic olefin is a norbornene derivative.

### Claim 14 (depends on 4)

A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 4, wherein the resin composition comprises at least one cyclic olefin.

### Claim 15 (depends on 14)

The ROMP composition according to claim 14, wherein the at least one cyclic olefin is a norbornene derivative.

### Claim 16 (depends on 8)

A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 8, wherein the resin composition comprises at least one cyclic olefin.

### Claim 17 (depends on 16)

The ROMP composition according to claim 16, wherein the at least one cyclic olefin is a norbornene derivative.