Ruthenium-or osmium-based complex catalysts

Patent metadata

Field	Value
Publication number	US-2018290134-A1
Application number	US-201615566373-A
Country	US
Kind code	A1
Filing date	Apr 12, 2016
Priority date	Apr 16, 2015
Publication date	Oct 11, 2018
Grant date	—

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.

First claim

1 . Complexes having the general formula (I)

wherein
M represents ruthenium or osmium,
X represents F, Cl, Br, I, —OH, —CF 3 , pyridine, —OC 6 H 5 , —CF 3 COO − , —CH 3 SO 3 − , or —BF 4 − ,
L 1 represents a N-heterocyclic carbene (NHC) ligand,
L 2 represents a phosphine ligand,
R 1 represents hydrogen,
R 2 represents
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.

2 . The complexes according to claim 1 , wherein:
M, L 1 , L 2 , X and R 1 have the same meanings as given in claim 1 , and R 2 represents

wherein R 3 , R 4 , R 5 , R 6 and R 7 are each individually of each other
H, NO 2 , F, Cl, Br, I or CN; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 ; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl; or
substituted or unsubstituted C 6 -C 14 -aryl; or
Pyren, Perylen, Benz(a)pyren; or
OR 12 , OC(═O)R 12 , C(═O)OR 12 , SO 3 R 12 , SO 3 N(R 12 ) 2 or SO 3 Na wherein R 12 represents H, straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl; or
(N(R 13 ) 3 ) + X − wherein X is halide, and R 13 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; 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.

3 . The complexes according to claim 1 , wherein the N-heterocyclic carbene ligand L 1 represents a cyclic carbene type ligand with at least one nitrogen as hetero atom being present in the ring, preferably based on imidazoline or imidazoline moieties

4 . (canceled)

5 . The complexes 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

6 . The complexes according to claim 1 , wherein
M represents ruthenium, L 1 represents IMes, SIMes, IPr or SIPr, L 2 represents PCy 3 or PPh 3 , X represents Cl, R 1 represents hydrogen, R 2 represents

wherein R 3 , R 4 , R 5 , R 6 and R 7 are each individually of each other hydrogen, —C(═O)OCH 3 , methoxy, ethoxy or iso-propoxy.

7 . The complexes according to claim 1 , wherein
M represents ruthenium, L 1 represents IMes or SIMes L 3 represents PCy 3 , X represents Cl, R 1 represents hydrogen, R 2 represents

wherein R 3 , R 4 , R 5 , R 6 and R 7 are each individually of each other hydrogen, methoxy, ethoxy or iso-propoxy.

8 . A process for preparing the complexes of general formula (I) according to claim 1 , the process comprising reacting a compound of general formula (1)
MHX(CO)L 1 L 2   (1)
wherein
M represents ruthenium or osmium,
X represents F, Cl, Br, I, —OH, —CF 3 , pyridine, —OC 6 H 5 , —CF 3 COO − , —CH 3 SO 3 − , or —BF 4 − ,
L 1 represents a N-heterocyclic carbene ligand,
L 2 represents a phosphine ligand,

with a compound of general formula (2)
R 1 —C≡C—R 2   (2)

wherein
R 1 represents hydrogen,
R 2 represents
H, NO 2 ; F, Cl, or Br; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl, preferably C 1 -C 8 -alkyl, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert.-butyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl, preferably C 5 -C 8 -cycloalkyl, more preferably cyclopentyl, cyclohexyl or cycloheptyl; or
substituted or unsubstituted C 8 -C 14 -aryl, preferably C 8 -C 10 -aryl, more preferably phenyl, which aryl group, more preferably phenyl is either unsubstituted or comprises 1, 2, 3, 4 or 5 identical or different substituents.

9 . The process according to claim 8 , comprising reacting a compound of general formula (1) wherein
M represents ruthenium or osmium, X represents F, Cl, Br, I, —OH, —CF 3 , pyridine, —OC 8 H 5 , —CF 3 COO − , —CH 3 SO 3 − , or —BF 4 − , L 1 represents a N-heterocyclic carbene ligand, and L 2 represents a phosphine ligand,
with a compound of general formula (2) wherein
R 1 represents hydrogen and
R 2 represents

wherein R 3 , R 4 , R 5 , R 6 and R 7 are each individually of each other
H, —NO, F, Cl, Br, I or —CN; or
straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl, preferably C 1 -C 8 -alkyl, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl; or
substituted or unsubstituted C 3 -C 10 -cycloalkyl, preferably C 5 -C 8 -cycloalkyl, more preferably cyclopentyl, cyclohexyl or cycloheptyl; or
substituted or unsubstituted C 6 -C 14 -aryl, preferably C 6 -C 10 -aryl, more preferably phenyl, which is either unsubstituted or comprises 1, 2, 3, 4 or 5 identical or different substituents; or
Pyren, Perylen, Benz(a)pyren; or
OR 12 , —OC(═O)R 12 , —C(═O)OR 12 , —SO 3 R 12 , —SO 3 N(R 12 ) 2 or —SO 3 Na wherein R 12 represents H, straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl, preferably C 1 -C 8 -alkyl, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl; or
—(N(R 13 ) 3 ) + X − wherein X is halide, preferably chloride, and R 13 are identical or different and represent H; straight chain or branched, substituted or unsubstituted C 1 -C 14 -alkyl, preferably C 1 -C 8 -alkyl, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert.-butyl; substituted or unsubstituted C 6 -C 14 -aryl, preferably C 6 -C 10 -aryl, more preferably phenyl, which-is either unsubstituted or comprises 1, 2, 3, 4 or 5 identical or different substituents; most preferably —N(CH 3 CH 3 )(C 2 H 5 ) 2 + Cl − , —N(C 2 H 5 ) 2 H + Cl − , —NH 3 + Cl − , —NH(CH 3 ) 2 + Cl − , or —N(CH 3 ) 3 + Cl − ; or
tris (C 1 -C 8 -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, preferably trisethoxysilyl-n-propyl.

10 . The process according to claim 8 , herein;
the compound of general formula (1) is selected from the group consisting of RuHCl(CO)(IMes)(PCy 3 ), RuHCl(CO)(SIMes)(PCy 3 ), RuHCl(CO)(IPr)(PCy 3 ), RuHCl(CO)(SIPr)(PCy 3 ), RuHCl(CO)(IMes)(PPh 3 ), RuHCl(CO)(SIMes)(PPh 3 ), RuHCl(CO)(IPr)(PPh 3 ) and RuHCl(CO)(SIPr)(PPh 3 ), 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-ethynylisophthala

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Wei Zhenli

Classifications

• C08L9/02

  Copolymers with acrylonitrile · CPC title

• B01J2231/645

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

• C08C19/02

  Hydrogenation · CPC title

• B01J31/20

  Carbonyls · CPC title

• B01J31/2291

  Olefins · CPC title