# US 10,441,948 B2 · Ruthenium-or osmium-based complex catalysts

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- Number: US 10,441,948 B2
- Document ID: US10441948B2
- Status: Granted
- Kind: B2
- Application number: 15/566,373
- Filed: 2016-04-12
- Published: 2018-10-11
- Granted: 2019-10-15
- Earliest claimed: 2015-04-16
- Assignees: Arlanxeo Deutschland GmbH
- Applicants: Arlanxeo Deutschland GmbH
- Inventors: Zhenli Wei
- Web page: https://patentgrep.com/patent/US10441948B2

## CPC

- B01J 31/2404: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring}
- B01J 31/20: Carbonyls
- B01J 31/2291: {Olefins}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- C07F 15/0046: {Ruthenium compounds}
- C08C 19/02: Hydrogenation
- C08L 9/02: Copolymers with acrylonitrile
- B01J 2231/645: of C=C or C-C triple bonds
- B01J 2531/821: Ruthenium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention relates to ruthenium- or osmium-based complex structures, to the synthesis thereof and their use as catalysts for hydrogenating unsaturated substrates.

## Claims

### Claim 1

A complex having the general formula (I)
wherein
M represents ruthenium or osmium,
X represents F, Cl, Br, I, —OH, —CF3, pyridine, —OC6H5, —CF3COO−, —CH3SO3−, or —BF4−,
L1 represents a N-heterocyclic carbene (NHC) ligand,
L2 represents a phosphine ligand,
R1 represents hydrogen,
R2 represents
straight chain or branched, substituted or unsubstituted C1-C14-alkyl; or
substituted or unsubstituted C3-C10-cycloalkyl; or
substituted or unsubstituted C6-C14-aryl.

### Claim 2 (depends on 1)

The complex according to claim 1, wherein:
M, L1, L2, X and R1 have the same meanings as given in claim 1, and
R2 represents
wherein R3, R4, R5, R6 and R7 are each individually of each other
H, NO2, F, Cl, Br, I or CN; or
straight chain or branched, substituted or unsubstituted C1-C14-alkyl; or
substituted or unsubstituted C3-C10-cycloalkyl; or
substituted or unsubstituted C5-C14-aryl; or
Pyren, Perylen, Benz(a)pyren; or
OR12, OC(═O)R12, C(═O)OR12, SO3R12, SO3N(R12)2 or SO3Na wherein R12 represents H, straight chain or branched, substituted or unsubstituted C1-C14-alkyl; or
(N(R13)3)+X− wherein X is halide, and R13 are identical or different and represent H; straight chain or branched, substituted or unsubstituted C1-C14-alkyl; substituted or unsubstituted C6-C14-aryl; or
tris (C1-C6-alkoxy)silyl-C1-C6-alkyl, tris (C6-C14-aryloxy)silyl-C1-C6-alkyl, or tris (C3-C10-cycloalkoxy)silyl-C1-C6-alkyl.

### Claim 3 (depends on 2)

The complex according to claim 2, wherein
wherein R3, R4, R5, R6 and R7 are each individually of each other
H, NO2, F, Cl, Br, I or CN; or
methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert.-butyl; or
cyclopentyl, cyclohexyl or cycloheptyl; or
unsubstituted phenyl, or phenyl comprising 1, 2, 3, 4 or 5 identical or different substituents; or
Pyren, Perylen, Benz(a)pyren; or
OR12, OC(═O)R12, C(═O)OR12, SO312, SO3N(R12)2 or SO3Na wherein R12 represents H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert.-butyl; or
N(CH3)(C2H5)2+Cl−, N(C2H5)2H+Cl−, NH3+Cl−, NH(CH3)2+Cl−, or N(CH3)3+Cl−; or trisethoxysilyl-n-propyl.

### Claim 4 (depends on 1)

The complex according to claim 1, wherein the N-heterocyclic carbene ligand L1 represents a cyclic carbene ligand with at least one nitrogen as hetero atom being present in the ring.

### Claim 5 (depends on 1)

The complex according to claim 1, wherein the NHC-ligand has the structures (IIIa) to (IIIu), where “Ph” stands in each case for phenyl, “Bu” stands in each case for butyl, i.e. either n-butyl, sec.-butyl, iso-butyl or tert.-butyl, “Mes” stands in each case for 2,4,6-trimethylphenyl, “Dipp” stands in each case for 2,6-diisopropylphenyl and “Dimp” stands in each case for 2,6-dimethylphenyl

### Claim 6 (depends on 1)

The complex according to claim 1, wherein
M represents ruthenium,
L1 represents N,N′-bis(mesityl)imidazole-2-ylidne, N,N′-bis(mesityl)imidazoldine-2-ylidene, N,N′-bis(2.6-diisopropylphenyl)imidazoline-2-ylidene or N,N′-bis(2,6-diisopropylphenyl)imidazolidine2-ylidene,
L2 represents PCy3 or PPh3,
X represents Cl,
R1 represents hydrogen,
R2 represents
wherein R3, R4, R5, R6 and R7 are each individually or each other hydrogen, —C(═O)OCH3, methoxy, ethoxy or iso-propoxy.

### Claim 7 (depends on 1)

The complex according to claim 1, wherein
M represents ruthenium,
L1 represents N,N′-bis(mesityl)imidazole-2-ylidne or N,N′-bis(mesityl)imidazolidine-2-ylidene,
L2 represents PCy3,
X represents Cl,
R1 represents hydrogen,
R2 represents
wherein R3, R4, R5, R6 and R7 are each individually of each other hydrogen, methoxy, ethoxy or iso-propoxy.

### Claim 8 (depends on 1)

The complex according to claim 1, wherein R2 represents:
methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert.-butyl; or
cyclopentyl, cyclohexyl or cycloheptyl; or
unsubstituted phenyl, or phenyl comprising 1, 2, 3, 4 or 5 identical or different substituents.

### Claim 9 (depends on 1)

The complex according to claim 1, wherein the N-heterocyclic carbene ligand L1 represents a structure corresponding to the general formulae (IIa) to (IIg):
wherein
R8, R9, R10 and R11 are identical or different and represent hydrogen, straight-chain or branched C1-C30-alkyl, C3-C20-cycloalkyl, C2-C20-alkenyl, C2-C20-alkynyl, C6-C24-aryl, C7-C25-alkaryl, C2-C20-heteroaryl, C2-C20-heterocyclyl, C1-C20-alkoxy, C2-C20-alkenyloxy, C2-C20-alkynyloxy, C6-C20-aryloxy, C2-C20-aralkoxycarbonyl, C1-C20-alkylthio, C6-C20-arylthio, —Si(R)3, —O—Si(R)3, —O—C(═O)R, C(═O)R, —C(═O)N(R)2, —NR—C(═O)—N(R)2, —SO2N(R)2, —S(═O)R, —S(═O)2R, —O—S(═O)2R, halogen, nitro or cyano; wherein in all above occurrences relating to the meanings of R8, R9, R10 and R11 the group R is identical or different and represents hydrogen, C1-C30-alkyl, C3-C20-cycloalkyl, C2-C20-alkenyl, C2-C20-alkynyl, C6-C24-aryl or C2-C20-heteroaryl, and wherein R8, R9, R10 and R11, independently of one another, are unsubstituted or substituted by one or more substituents selected from straight-chain or branched C1-C10-alkyl, C3-C8-cycloalkyl, C1-C10-alkoxy, C6-C24-aryl, C2-C20 heteroaryl, C2-C20 heterocyclic, a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein the abovementioned substituents are independently of one another either unsubstituted or substituted by one or more
substituents selected from the group consisting of chlorine or bromine, C1-C5-alkyl, C1-C5-alkoxy and phenyl.

### Claim 10 (depends on 9)

The complex according to claim 9, wherein
R8 and R9 are identical or different and represent hydrogen, C6-C24-aryl, straight-chain or branched C1-C10-alkyl, or form a cycloalkyl or aryl structure together with the carbon atoms to which they are bound, and
R10 and R11 are identical or different and represent straight-chain or branched C1-C10-alkyl, C3-C10-cycloalkyl, substituted or unsubstituted C6-C24-aryl, C1-C10-alkylsulfonate, or C8-C10-arylsulfonate.

### Claim 11 (depends on 9)

The complex according to claim 9, wherein
R8 and R9 are identical or different and represent hydrogen, phenyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, and iso-butyl, or form a cycloalkyl or aryl structure together with the carbon atoms to which they are bound, and
R10 and R11 are identical or different and represent iso-propyl or n-pentyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, C1-C10-alkyisulfonate, or C6-C10-arylsulfonate.

### Claim 12 (depends on 1)

A process of preparing the complex of the general formula (I) according to claim 1, the process comprising the step of: reacting a compound of general formula (1)
MHX(CO)L1L2 (1)
wherein
M represents ruthenium or osmium,
X represents F, Cl, Br, I, —OH, —CF3, pyridine, —OC6H5, —CF3COO−, —CH3SO3−, or —BF4−,
L1 represents a N-heterocyclic carbene ligand,
L2 represents a phosphine ligand,
with a compound of general formula (2)
R1—C≡C—R2 (2)
wherein
R1 represents hydrogen,
R2 represents
H, NO2−, F, Cl, or Br; or
straight chain or branched, substituted or unsubstituted C1-C14-alkyl; or
substituted or unsubstituted C3-C10-cycloalkyl; or
substituted or unsubstituted C8-C14-aryl.

### Claim 13 (depends on 12)

The process according to claim 12, comprising the step of:
reacting a compound of general formula (1) wherein
M represents ruthenium or osmium,
X represents F, Cl, Br, I, —OH, —CF3, pyridine, —OC6H5, —CF3COO−, —CH3SO3−, or —BF4−,
L1 represents a N-heterocyclic carbene ligand, and
L2 represents a phosphine ligand,
with a compound of general formula (2) wherein
R1 represents hydrogen and
R2 represents
wherein R3, R4, R5, R6 and R7 are each individually of each other H, —NO2, F, Cl, Br, I or —CN; or
straight chain or branched, substituted or unsubstituted C1-C14-alkyl; or
substituted or unsubstituted C3-C10-cycloalkyl; or
substituted or unsubstituted C6-C14-aryl; or
Pyren, Perylen, Benz(a)pyren; or
—OR12, —OC(═O)R12, —C(═O)OR12, —SO3R12, —SO3N(R12)2 or —SO3Na wherein R12 represents H, straight chain or branched, substituted or unsubstituted C1-C14-alkyl; or
—(N(R13)3)+X− wherein X is halide, and R13 are identical or different and represent H; straight chain or branched, substituted or unsubstituted C1-C14-alkyl, substituted or unsubstituted C6-C14-aryl; or
tris (C1-C8-alkoxy)silyl-C1-C6-alkyl, tris (C6-C14-aryloxy)silyl-C1-C6-alkyl, or tris (C3-C10-cycloalkoxy)silyl-C1-C6-alkyl, or trisethoxysilyl-n-propyl.

### Claim 14 (depends on 12)

The process according to claim 12, wherein:
the compound of general formula (1) is selected from the group consisting of;
RuHCl(CO)(N,N′-bis(mesity)imidazole-2-ylidne)(PCy3), RuHCl(CO)(N,N′-bis(mesityl)imidazolidine-2-ylidene)(PCy3), RuHCl(CO)(IPr)(PCy3), RuHCl(CO)(N,N′-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene)(PCy3), RuHCl(CO)(N,N′-bis(mesityl)imidazole-2-ylidne)(PPh3), RuHCl(CO)(N,N′-bis(mesityl)imidazolidine-2-ylidene)(PPh3), RuHCl(CO)(IPr)(PPh3) and RuHCl(CO)(N,N′-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene)(PPh3, and,
the compound of general formula (2) is selected from the group consisting of;
phenyl acetylene, 1-Ethynyl-2-isopropoxybenzene, 1-Ethynyl-3-isopropoxybenzene, 2-Ethynylanisole, 3-Ethynylanisole, 4-Ethynylanisole, 1-Ethynyl-3,5-dimethoxybenzene and Dimethyl-5-ethynylisophthalate.

### Claim 15 (depends on 1)

A process of preparing partially or fully saturated compounds, the process comprising the step of: contacting unsaturated compounds comprising at least one C═C double bond with hydrogen in the presence of the complex according to claim 1.

### Claim 16 (depends on 1)

A process of preparing partially or fully hydrogenated nitrite rubbers comprising the step of: bringing a solution of unsaturated nitrile rubber, or bringing a latex of unsaturated nitrile rubber in contact with hydrogen in the presence of the complex according to claim 1.

### Claim 17 (depends on 16)

The process according to claim 16, whereas nitrile rubbers represent copolymers or terpolymers comprising repeating units based on (i) at least one conjugated diene, (ii) at least one α,β-unsaturated nitrile monomer.

### Claim 18 (depends on 16)

The process according to claim 16, wherein the process comprises the step of: bringing a latex of unsaturated nitrile rubber in contact with hydrogen, and further comprises the step of preparing the latex in an aqueous emulsion polymerization process.