# US 2014/0155621 A1 · Methods for preparing ruthenium carbene complexes and precursors thereto

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- Number: US 2014/0155621 A1
- Document ID: US20140155621A1
- Status: Published application
- Kind: A1
- Application number: 14/087,954
- Filed: 2013-11-22
- Published: 2014-06-05
- Earliest claimed: 2012-11-30
- Assignees: Elevance Renewable Sciences, Inc.
- Applicants: Elevance Renewable Sciences, Inc.
- Inventors: Linda A. Kunz; Steven A. Cohen
- Web page: https://patentgrep.com/patent/US20140155621A1

## CPC

- C07F 15/0046: {Ruthenium compounds}
- B01J 31/2278: {Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts}
- B01J 31/2265: {Carbenes or carbynes, i.e.(image)}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 2231/543: alkene metathesis
- B01J 2531/821: Ruthenium
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Methods of preparing ruthenium carbene complex precursors are disclosed herein. In some embodiments, the methods include reacting a ruthenium refinery salt with an L-type ligand and a reducing agent to form the ruthenium carbene complex precursor. Methods of preparing a ruthenium vinylcarbene complex are also disclosed. In some embodiments, preparing a ruthenium carbene complex includes converting a ruthenium carbene complex precursor into a ruthenium carbene complex having a structure (PR1R2R3)2Cl2Ru═CH—R4, wherein R1, R2, R3, and R4 are defined herein.

## Claims

### Claim 1

A method for preparing a ruthenium carbene complex precursor comprising:
reacting a ruthenium refinery salt with an L-type ligand and a reducing agent to form the ruthenium carbene complex precursor.

### Claim 2 (depends on 1)

The method of claim 1, wherein the L-type ligand is an olefin, a phosphine, a phosphite, an amine, CO, N2, or a combination thereof.

### Claim 3

(canceled)

### Claim 4 (depends on 2)

The method of claim 2, wherein the L-type ligand comprises a cyclic olefin.

### Claim 5

(canceled)

### Claim 6 (depends on 4)

The method of claim 4, wherein the cyclic olefin is cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, cyclodecadiene, cycloundecadiene, cyclododecadiene, cyclododecatriene, paramenthadiene, phellandrene, norbornadiene, terpinene, limonene, or a combination thereof.

### Claim 7

(canceled)

### Claim 8 (depends on 4)

The method of claim 4, wherein the cyclic olefin comprises cyclooctadiene.

### Claim 9 (depends on 2)

The method of claim 2, wherein the L-type ligand comprises a phosphorus-containing ligand having a structure PR1R2R3;
wherein R1, R2, and R3 are alike or different and are each independently selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C1-C10 alkoxy, and combinations thereof; and
wherein covalent bonds may optionally exist between two or more of R1, R2, and R3; and
wherein any two of R1, R2, and R3 taken together may optionally form a ring with the phosphorus atom.

### Claim 10 (depends on 9)

The method of claim 9 wherein the phosphorus-containing ligand comprises triphenyl phosphine.

### Claim 11 (depends on 1)

The method of claim 1, wherein the ruthenium refinery salt comprises (NH4)2RuCl5, (NH4)2RuCl5.H2O, polyhydrated (NH4)2RuCl5, (NH4)4[Ru2OCl10], or a combination thereof.

### Claim 12 (depends on 11)

The method of claim 11, wherein the ruthenium refinery salt further comprises NH4Cl.

### Claim 13 (depends on 12)

The method of claim 12, wherein the method further comprises removing at least a portion of the NH4Cl from the ruthenium refinery salt prior to the reacting.

### Claim at position 14

14-22. (canceled)

### Claim 23 (depends on 1)

The method of claim 1, wherein the reducing agent comprises a metal selected from the group consisting of Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements, and combinations thereof.

### Claim 24 (depends on 23)

The method of claim 23, wherein the reducing agent comprises FeCl2 or a hydrated form thereof.

### Claim 25 (depends on 23)

The method of claim 23 wherein the reducing agent comprises CoCl2 or a hydrated form thereof.

### Claim 26

(canceled)

### Claim 27 (depends on 1)

The method of claim 1, wherein the reducing agent is present at a loading of at least about 1 molar equivalent relative to ruthenium in the ruthenium refinery salt.

### Claim at position 20

28-29. (canceled)

### Claim 30 (depends on 1)

The method of claim 1, wherein the reacting of the ruthenium refinery salt with the L-type ligand and the reducing agent is performed in an alcoholic solvent.

### Claim at position 22

31-33. (canceled)

### Claim 34 (depends on 1)

The method of claim 1, wherein the reacting of the ruthenium intermediate with the L-type ligand and the reducing agent comprises a reaction time of at least about 5 hours.

### Claim at position 24

35-39. (canceled)

### Claim 40 (depends on 1)

The method of claim 1, wherein the ruthenium carbene complex precursor comprises a material having a structure [RuCl2(COD)]x, wherein x is an integer value of 1 or more.

### Claim 41 (depends on 1)

The method of claim 1, wherein the ruthenium carbene complex precursor comprises a material having a structure RuCl2(PR1R2R3)3;
wherein R1, R2, and R3 are alike or different and are each independently selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C1-C10 alkoxy, and combinations thereof; and
wherein covalent bonds may optionally exist between two or more of R1, R2, and R3; and
wherein any two of R1, R2, and R3 taken together may optionally form a ring with the phosphorus atom.

### Claim 42 (depends on 1)

The method of claim 1, wherein the reacting of the ruthenium refinery salt with the L-type ligand and the reducing agent is performed in a non-reactive solvent or in a solvent mixture that comprises one or a plurality of non-reactive solvents.

### Claim 43

(canceled)

### Claim 44 (depends on 42)

The method of claim 42, wherein the solvent mixture further comprises one or a plurality of alcohols.

### Claim 45 (depends on 42)

The method of claim 42, wherein the non-reactive solvent comprises an alkane.

### Claim at position 31

46-47. (canceled)

### Claim 48

A method for preparing a ruthenium carbene complex precursor comprising:
reacting a ruthenium refinery salt with an L-type ligand and a reducing agent to form the ruthenium carbene complex precursor;
wherein the L-type ligand comprises cyclooctadiene or a phosphorus-containing material having a structure PR1R2R3;
wherein the ruthenium refinery salt comprises a material selected from the group consisting of (NH4)2RuCl5, (NH4)2RuCl5.H2O, polyhydrated (NH4)2RuCl5, (NH4)4[Ru2OCl10], and combinations thereof;
wherein the reducing agent comprises a metal selected from the group consisting of Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements, and combinations thereof;
wherein the ruthenium carbene complex precursor comprises a compound having a structure [RuCl2(COD)]x or a compound having a structure RuCl2(PR1R2R3)3;
wherein x is an integer value of 1 or more;
wherein R1, R2, and R3 are alike or different and are each independently selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C1-C10 alkoxy, and combinations thereof; and
wherein covalent bonds may optionally exist between two or more of R1, R2, and R3; and
wherein any two of R1, R2, and R3 taken together may optionally form a ring with phosphorus.

### Claim 49 (depends on 48)

The method of claim 48, wherein the reducing agent is selected from the group consisting of FeCl2, CoCl2, hydrated forms thereof, and combinations thereof.

### Claim 50 (depends on 4)

A method for preparing a ruthenium vinylcarbene complex comprising:
converting a ruthenium carbene complex precursor prepared according to the method of claim 4 into a ruthenium hydrido halide complex; and
reacting the ruthenium hydrido halide complex with a propargyl halide to form the ruthenium vinylcarbene complex.

### Claim at position 35

51-58. (canceled)

### Claim 59 (depends on 9)

A method for preparing a ruthenium carbene complex comprising:
converting a ruthenium carbene complex precursor prepared according to the method of claim 9 into a ruthenium carbene complex having a structure (PR1R2R3)2X1X2Ru═CH—R4;
wherein X1 and X2 are halogen atoms that are each independently selected from the group consisting of F, Cl, Br, and I;
wherein R1, R2, R3, and R4 are alike or different, and are each independently selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C1-C10 alkoxy, and combinations thereof; and
wherein covalent bonds may optionally exist between two or more of R1, R2, and R3; and
wherein any two of R1, R2, and R3 taken together may optionally form a ring with phosphorus.

### Claim at position 37

60-64. (canceled)

### Claim 65

A method of preparing a product that comprises [RuCl2(COD)]x, the method comprising:
reacting a ruthenium refinery salt with cyclooctadiene and a reducing agent in an alcoholic solvent under reflux conditions to form the product;
wherein x is an integer value of 1 or more;
wherein the ruthenium refinery salt comprises a material selected from the group consisting of (NH4)2RuCl5, (NH4)2RuCl5.H2O, polyhydrated (NH4)2RuCl5, (NH4)4[Ru2OCl10], and combinations thereof; and
wherein the reducing agent comprises a metal selected from the group consisting of Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements, and combinations thereof.

### Claim at position 39

66-76. (canceled)