# US 2014/0155642 A1 · Ruthenium complexes comprising paracyclophane and carbonyl ligands, and their use as catalyst

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- Number: US 2014/0155642 A1
- Document ID: US20140155642A1
- Status: Published application
- Kind: A1
- Application number: 14/005,436
- Filed: 2012-03-16
- Published: 2014-06-05
- Earliest claimed: 2011-03-17
- Assignees: Johnson Matthey Public Limited Company
- Inventors: Damian Mark Grainger; Hans Guenter Nedden; Stephen James Roseblade
- Web page: https://patentgrep.com/patent/US20140155642A1

## CPC

- C07F 15/0053: {without a metal-carbon linkage}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- C07F 15/0046: {Ruthenium compounds}
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2231/52: Isomerisation reactions
- B01J 2231/60: Reduction reactions, e.g. hydrogenation
- B01J 2531/0263: Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes
- 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

The present invention relates to the ruthenium complexes comprising paracyclophane and carbonyl ligands, methods for the preparation thereof and uses of the complexes in isomerisation, hydrogenation, transfer hydrogenation, hydroformylation and carbonylation reactions.

## Claims

### Claim 1

A ruthenium complex of formula (1a), (1b), (1c) or (1d):
[Ru Hal2 L CO S] (1a)
[Ru2 Hal4 L2 (CO)2] (1b)
[Ru2 Hal4 L2 (CO)] (1c)
[Ru Hal2 L (CO)2] (1d)
wherein:
Hal is a halogen ligand,
L is a substituted or unsubstituted paracyclophane ligand of formula (2):
wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms,
each Y1, Y2, Y3 and Y4 are independently selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl,
each Z1, Z2 and Z3 are the same or different and are substituting groups that optionally contain functional groups,
a, b, c, d, e and f are the integers 0 or 1 and a+b+c+d+e+f=0 to 6;
CO is a carbonyl ligand; and
S is a solvent ligand.

### Claim 2 (depends on 1)

A ruthenium complex according to claim 1 wherein X1 and X2 are both —C2H4—.

### Claim 3 (depends on 1)

A ruthenium complex according to claim 1, wherein each Y1, Y2, Y3 and Y4 are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, naphthyl, anthracyl, 4-methylphenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 4-methoxy-3,5-diisopropylphenyl, 4-methoxy-3,5-ditertbutylphenyl, 3,5-diisopropylphenyl, 3,5-ditertbutylphenyl, 4-dimethylamino-3,5-dimethylphenyl, 4-dimethylamino-3,5-diisopropylphenyl, 4-dimethylamino-3,5-ditertbutylphenyl and fluorenyl.

### Claim 4 (depends on 1)

A ruthenium complex according to claim 1, wherein Z1, Z2 and Z3 are independently substituting groups selected from C1-C30 branched or linear alkyl or phenyl, naphthyl or anthracyl groups.

### Claim 5 (depends on 1)

A ruthenium complex according to claim 1 wherein Z1, Z2 or Z3 are independently substituting groups comprising one or more functional groups selected from halide, hydroxyl, alkoxy, silyloxy, aralkyloxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, mercapto, sulphide, amino, amine, imine, amide and imide.

### Claim 6 (depends on 1)

A ruthenium complex according to claim 1, wherein a+b+c+d+e+f=1 or 2.

### Claim 7 (depends on 1)

A ruthenium complex according to claim 1, wherein a+b+c=1 and/or d+e+f=1.

### Claim 8 (depends on 1)

A ruthenium complex according to claim 1, wherein a+b+c+d+e+f=0.

### Claim 9 (depends on 1)

A ruthenium complex according to claim 1, wherein S is a solvent ligand selected from the group consisting of amides, N-heterocyles, ketones, alcohols, esters, aromatic solvents, chlorinated alkanes, formic acid, dimethylsulfoxide and acetonitrile.

### Claim 10 (depends on 1)

A ruthenium complex according to claim 1, wherein the complex of formula (1a) is a solid and further comprises a co-crystallised solvent.

### Claim 11 (depends on 1)

A method for the preparation of a ruthenium complex of formula (1a) according to claim 1, comprising the step of:
(a) reacting polymeric [Ru Hal2 (CO)2] n or [Ru Hal2 (CO)3]2 with a paracyclophane ligand of formula (2) in a solvent S to form the complex of formula (1a); or
(b) heating a complex of formula (lb) in a solvent S to form the complex of formula (1a); or
(c) reacting [Ru (arene) Hal2]2 with a paracyclophane ligand of formula (2) in a solvent S to form the complex of formula (1a), wherein at least a portion of the solvent S decarbonylates to form CO.

### Claim 12 (depends on 1)

A method for the preparation of the ruthenium complex of formula (lb) according to claim 1, comprising the step of reacting polymeric [Ru (Hal)2 CO (H2O)]n with a paracylophane ligand of formula (2) in a solvent mixture comprising at least one alcohol and chlorinated alkane to form the complex of formula (1b).

### Claim 13 (depends on 1)

A method for the preparation of the ruthenium complex of formula (1c) according to claim 1, comprising the steps of:
(a) reacting [Ru (arene) Hal2]2 with a paracyclophane ligand of formula (2) in a solvent S; and
(b) reacting the product of step (a) with a ruthenium complex of formula (1a) in a solvent S to form the ruthenium complex of formula (1c).

### Claim 14 (depends on 1)

A method for the preparation of the ruthenium complex of formula (1d) according to claim 1, comprising the step of reacting polymeric [Ru Hal2 (CO)2]n, with a paracyclophane ligand of formula (2) in a solvent S to form the complex of formula (1d).

### Claim 15 (depends on 1)

A method for performing isomerisation, hydrogenation, transfer hydrogenation, hydroformylation or carbonylation reactions, comprising utilizing a ruthenium complex according to claim 1 as a catalyst for said reactions.

### Claim 16 (depends on 2)

A ruthenium complex according to claim 2, wherein Z1, Z2 and Z3 are independently substituting groups selected from C1-C30 branched or linear alkyl or phenyl, naphthyl or anthracyl groups.

### Claim 17 (depends on 2)

A ruthenium complex according to claim 2 wherein Z1, Z2 or Z3 are independently substituting groups comprising one or more functional groups selected from halide, hydroxyl, alkoxy, silyloxy, aralkyloxy, carbonyl, carboxyl, anhydride, methacryl, epoxide, vinyl, nitrile, nitro, sulphate, sulphonyl, mercapto, sulphide, amino, amine, imine, amide and imide.

### Claim 18 (depends on 2)

A ruthenium complex according to claim 2, wherein a+b+c+d+e+f=1 or 2.

### Claim 19 (depends on 2)

A ruthenium complex according to claim 2, wherein a+b+c=1 and/or d+e+f=1.

### Claim 20 (depends on 2)

A ruthenium complex according to claim 2, wherein a+b+c+d+e+f=0.