Ruthenium- or osmium-based complex catalysts

Patent metadata

Field	Value
Publication number	US-9802972-B2
Application number	US-201414896412-A
Country	US
Kind code	B2
Filing date	Jun 6, 2014
Priority date	Jun 9, 2013
Publication date	Oct 31, 2017
Grant date	Oct 31, 2017

Abstract

The present invention provides novel ruthenium or osmium based complex structures with a unique combination of ligands comprising a Schiff-base type ligand, a N-heterocyclic carbene ligand and a CO ligand which can be prepared according to two different routes involving easily accessible starting materials and which represent excellent catalysts for hydrogenating unsaturated compounds, oligomers and polymers, in particular at unforeseeably low temperatures.

First claim

The invention claimed is:

1. A complex having the general formula (I)

wherein:
M is ruthenium or osmium;
Y represents H, F, Cl, Br, I, CF 3 , pyridine, —OC 6 H 5 , CF 3 COO—, CH 3 SO 3 —, or BF 4 ;
R 1 , R 2 , R 3 , and R 4 are identical or different and represent
H; NO 2 ; CF 3 ; halogen; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 substituents; or
OR 7 , OC(═O)R 7 , CO(═O)R 7 , SO 3 R 7 , SO 3 N(R 7 ) 2 or SO 3 Na wherein R 7 represents H, straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
(N(R 8 ) 3 ) + X − wherein X is halide, and R 8 are identical or different and represent H; straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl, substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 substituents; or
tris (C 1 -C 6 -alkoxy)silyl-C 1 -C 6 -alkyl, tris (C 6 -C 14 -aryloxy)silyl-C 1 -C 6 -alkyl, or tris(C 3 -C 10 -cycloalkoxy)silyl-C 1 -C 6 -alkyl;

R 5 represents H; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents; and

R 6 represents H, or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 substituents.

2. The complex of general formula (I) according to claim 1 , wherein:
M is ruthenium;
Y is H or Cl;
R 1 , R 2 , R 3 , and R 4 are identical or different and represent
H; NO 2 ; F, Cl, or Br; or
straight chain or branched, substituted or unsubstituted C 1 -C 8 -alkyl; or
substituted or unsubstituted C 5 -C 8 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents; or
OR 7 , OC(═O)R 7 , CO(═O)R 7 , SO 3 R 7 , SO 3 N(R 7 ) 2 or SO 3 Na wherein R 7 represents H, straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl;

R 5 represents H; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents; and

R 6 represents H, or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents.

3. The complex of general formula (I) according to claim 1 , wherein:
M is ruthenium,
Y is H or Cl,
R 1 , R 2 , R 3 , and R 4 are all H or R 1 , R 3 , and R 4 are all H while R 2 is simultaneously NO 2 ;
R 5 represents H;
straight chain or branched, substituted or unsubstituted C 1 -C 8 -alkyl; or
substituted or unsubstituted C 5 -C 8 -cycloalkyl; or
substituted or unsubstituted C 6 -C 10 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents; and

R 6 represents H, or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents.

4. The complex of the general formula (I) according to claim 1 , wherein the N-heterocyclic carbene ligand comprises a cyclic carbene type ligand based on imidazoline or imidazolidine moieties and having at least one nitrogen as hetero atom present in the ring.

5. The complex according to claim 4 , wherein, in the N-heterocyclic carbene ligand in the complex of the general formula (I),
R 6 and R 9 are identical or different and represent hydrogen, C 6 -C 24 -aryl, or form a cycloalkyl or aryl structure together with the carbon atoms to which they are bound, and
R 10 and R 11 are identical or different represent straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, substituted or unsubstituted C 6 -C 24 -aryl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, C 1 -C 10 -alkylsulfonate, or C 6 -C 10 -arylsulfonate.

6. The complex according to claim 1 , wherein the N-heterocyclic carbene ligand in the complex of the general formula (I) has the structures (IIIa) to (IIIu), where “Ph” means in each case phenyl, “Bu” means in each case butyl, “Mes” represents in each case 2,4,6-trimethylphenyl, “Dipp” means in all cases 2,6-diisopropylphenyl, and “Dimp” means in each case 2,6-dimethylphenyl

7. The complex according to claim 1 , wherein the complex of general formula (I) is selected from the group consisting of (Ia)-IMes, (Ia)-SIMes, (Ia)-IPr, (Ib)-IMes, (Ib)-SIMes, (Ib)-IPr, (Ic)-IMes, (Ic)-SIMes, (Ic)-IPr, wherein “IMes” means N,N′-bis(mesityl)imidazol-2-ylidene, “SIMes” means N,N′-bis(mesityl)imidazolidin-2-ylidene, “IPR” means N,N′-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene and “ItBu” means N,N′-bis(tert-butyl)imidazol-2-ylidene,

8. A process for preparing the complex of general formula (I) according to claim 1 , the process comprising:
reacting a compound of general formula (1)
MXY(CO)(PR 3 ) n   (1)

wherein:
M is ruthenium or osmium;
X is H, Cl, Br or I;
Y represents H, F, Cl, Br, I, CF 3 , pyridine, —OC 6 H 5 , CF 3 COO—, CH 3 SO 3 —, or BF 4 ;
R represents
substituted or unsubstituted C 1 -C 14 -alkyl;
substituted or unsubstituted C 3 -C 8 -cycloalkyl;
substituted or unsubstituted C 6 -C 14 -aryl; and

n is 3, if R represent substituted or unsubstituted C 6 -C 14 -aryl; or
n is 2, if R represent substituted or unsubstituted C 1 -C 14 -alkyl, or substituted or unsubstituted C 3 -C 8 -cycloalkyl;

with a compound of general formula (2)

wherein
R 1 , R 2 , R 3 , and R 4 are identical or different and represent
H; NO 2 ; CF 3 ; halogen; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl;
substituted or unsubstituted C 3 -C 10 -cycloalkyl;
substituted or unsubstituted C 6 -C 14 -aryl, which aryl group is either unsubstituted or contains 1, 2, 3, 4 or 5 identical or different substituents;
OR 7 , OC(═O)R 7 , CO(═O)R 7 , SO 3 R 7 , SO 3 N(R 7 ) 2 or SO 3 Na wherein R 7 represents H, straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl;
(N(R 8 ) 3 ) + X − wherein X is halide, and R 8 are identical or different and represent H; straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl, substituted or unsubstituted C 6 -C 14 -aryl, which aryl

Assignees

• Lanxess Deutschland Gmbh
• Arlanxeo Deutschland Gmbh

Inventors

• Wei Zhenli
• Liu Qingchun

Classifications

• B01J31/2217

  At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title

• B01J2231/645

  of C=C or C-C triple bonds · CPC title

• C08C19/02

  Hydrogenation · CPC title

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title

• C07F15/0046 Primary

  Ruthenium compounds · CPC title