Ruthenium-based complex catalysts

Patent metadata

Field	Value
Publication number	US-9828401-B2
Application number	US-201214238270-A
Country	US
Kind code	B2
Filing date	Aug 15, 2012
Priority date	Aug 15, 2011
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

The present invention provides novel Ruthenium-based transition metal complex catalysts comprising specific ligands, their preparation and their use in hydrogenation processes. Such complex catalysts are inexpensive, thermally robust, and olefin selective.

First claim

The invention claimed is:

1. A Ruthenium-based complex catalyst according to general formula (I)

wherein
X 1 and X 2 are identical or different and represent anionic ligands,
X 3 represents a non-coordinating anion,
t is 1,
t′ is either 0 or 1,
u is 1,
L 1 , L 2 and L 3 represent identical or different ligands, wherein at least one of L 1 , L 2 and L 3 represents either a ligand having the general structure (Ia*) or (Ib*)

 or a ligand having the general structure (Ic*) or (Id*)

 in which formulae (Ia*), (Ib*), (Ic*) and (Id*)
n is identical or different and represents an integer of 1 to 20,
D is identical or different and represents hydroxy, alkoxy, aryloxy, thiol, thiolate, thioether, seienol, selenoether, amine, phosphine, phosphate, phosphite, arsine, suifoxide, sulfone, phosphinimine, aminophosphine, carbene, selenoxide, imidazoline, imidazolidine, phosphine oxide, phosphine sulfide, phosphine selenide, ketone, ester, pyridyl, substituted pyridyl or any moiety able of acting as a two electron donor,
R is identical or different and represents H, alkyl or aryl, and
E is identical or different and represents a divalent moiety able of acting as a two electron donor selected from the group consisting of —O—, —S—, —Se—, —N(R)—, —P(R)—, —As(R)—, —S(═O)—, —PR(═S)—, —PR(═O)—, —C(═O)—, —C(═S)—, 2,6-pyridylene, substituted 2,6-pyridylene and any other divalent moiety able of acting as a two electron donor, and
R 5 are identical or different in a respective moiety (Ia*), (Ib*), (Ic*) or (Id*) and represent H, alkyl, aryl, halide, or in the alternative two R 5 together with the two adjacent carbon atoms to which they are bound in a moiety (Ia*), (Ib*), (Ic*) or (Id*) form a fused-on five- or six-membered saturated or unsaturated ring.

2. The ruthenium-based complex catalyst according to claim 1 , having the general formula (I)

wherein
X 1 , X 2 are identical or different and represent anionic ligands,
X 3 represents a non-coordinating anion,
t is 1,
t′ is either 0 or 1,
u is 1, and
L 1 , L 2 , L 3 represent identical or different ligands, wherein at least one of L 1 , L 2 and L 3 represents either a ligand having the general structure (Ia) or (Ib)

 or a ligand having the general structure (Ic) or (Id)

 in which formulae (Ia), (Ib), (Ic) and (Id)
n is identical or different and represents an integer of 1 to 20,
D is identical or different and represents hydroxy, alkoxy, aryloxy, thiol, thiolata, thioether, selenol, salenoether, amine, phosphine, phosphate, phosphite, arsine, sulfoxide, sulfone, phosphinimine, aminophosphine, carbene, seienoxide, imidazoline, imidazolidine, phosphine oxide, phosphine sulfide, phosphine selenide, ketone, ester, pyridyl, substituted pyridyl or any moiety able of acting as a two electron donor,
R is identical or different and represents H, alkyl or aryl, and
E is identical or different and represents a divalent moiety able of acting as a two electron donor selected from the group consisting of —O—, —S—, —Se—, —N(R)—, —As(R)—, —S(═O)—, —PR(═S)—, —PR(═O)—, —C(═O)—, —C(═S)—, 2,6-pyridylene, substituted 2,6-pyridylene and any other divalent moiety able of acting as a two electron donor.

3. The catalyst according to claim 2 , wherein:
L 1 , L 2 , L 3 represent identical or different ligands, wherein at least one of L 1 , L 2 and L 3 represents either a ligand having the general structure (Ia) or (Ib) or a ligand having the general structure (Ic) or (Id) and wherein
n, R and E have the same meanings as given in claim 2 , and
D is identical or different and represents hydroxy, alkoxy, aryloxy, thiol, thiolate, thioether, suifoxide, sulfone, phosphine oxide, phosphine sulfide, ketone, ester, or any moiety able of acting as a two electron donor.

4. A ruthenium-based complex catalyst according to general formula (I)

in which:
X 1 , X 2 are identical or different and represent hydride, halide, pseudohalide, aikoxide, amide, tosylate, inflate, phosphate, borate, carboxylate, acetate, halogenated acetate, halogenated alkylsulfonate, or a weakly coordinating anion,
X 3 represents a non-coordinating anion,
t is 1,
t′ is either 0 or 1,
u is 1,
one ligand of L 1 , L 2 , and L 3 has the general structure according to formulae (Ia) or (Ib),

wherein
n is identical or different and represents an integer of 1 to 20,
D is identical or different and represents hydroxy, alkoxy, myloxy, thiol, thioiate, thioether, seienol, selerioether, amine, phosphine, phosphate, arsine, sulfoxide, sulfone, alkyl, phosphinimine, aminophosphine, carbene, selenoxide, imidazoline, imidazoltdine, phosphine oxide, phosphine sulfide, phosphine selenide, ketone, ester, pyridyl, substituted pyridyl, or any other moiety able of acting as a two electron donor,
R is identical or different and represents H, alkyl or aryl,
E is identical or different and represents a divalent moiety able of acting as a two electronted from the group consisting of —O—, —S—, —Se—, —N(R)—, —P(R)—, —As(R)—, —S(═O)—, —PR(═S)—, —PR(═O)—, —C(═O)—, —C(═S)—, 2,6-pyridylene, substituted 2,6-pyridylene and any other divalent moiety able of acting as a two electron donor, and

the remainder ligand(s) of L 1 , L 2 , and L 3 being a ligand/ligands different from the one of formulae (Ia) and (Ib).

5. The catalyst according to claim 2 , in which:
X 1 , X 2 are identical or different and represent hydride, halide, pseudohalide, alkoxide, amide, tosylate, triflate, phosphate, borate, carboxylate, acetate, halogenated acetate, halogenated alkylsulfonate, or a weakly coordinating anion,
one ligand of L 1 , L 2 , and L 3 has the general structure according to formulae (Ia) or (Ib),
wherein
n is identical or different and represents an integer of 1 to 5,
D is identical or different and represents C 1 -C 10 alkoxy or C 6 -C 14 aryloxy,

with the remainder ligand(s) of L 1 , L 2 , and L 3 being a ligand/ligands different from the one of formulae (Ia) and (Ib), and selected from the group consisting of PPh 3 , P(p-Tol) 3 , P(o-Tol) 3 , PPh(CH 3 ) 2 , P(CF 3 ) 3 , P(p-FC 6 H 4 ) 3 , P(p-CF 3 C 6 H 4 ) 3 , P(C 6 H 4 —SO 3 Na) 3 , P(CH 2 C 6 H 4 —SO 3 Na) 3 , P(isopropyl) 3 , P(CHCH 3 (CH 2 CH 3 )) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 , P(benzyl) 3 , and an imidazoline or imidazolidine ligand having the general formulae (IIa), or (IIb),

wherein, under the proviso that the ligand(s) according to formulae (IIa) and (IIb) are different from those of the general formulae (Ia), (Ib), (Ic) and (Id),
R 1 , R 2 , R 3 , R 4 are identical or different and are each hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -car

Assignees

• Jeschko Julia Maria
• Stephan Douglas
• Lund Clinton
• Sgro Michael
• Ong Christopher
• Cariou Renan
• Arlanxeo Deutschland Gmbh
• The Governing Council Of Univ Of Toronto

Inventors

• Jeschko Julia Maria
• Stephan Douglas
• Lund Clinton
• Sgro Michael
• Ong Christopher
• Cariou Renan

Classifications

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• C07C231/12

  by reactions not involving the formation of carboxamide groups · CPC title

• C07C211/06

  containing only n- or iso-propyl groups · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• C07C5/09

  to carbon-to-carbon double bonds · CPC title