Ruthenium-based complex catalysts
View Patent ↗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.
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 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 20 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 6 -C 20 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 20 -arylsulphonate, or C 1 -C 20 -alkylsulphinyl,
or in the alternative,
R 3 and R 4 have the above mentioned meanings and R 1 and R 2 jointly form a C 6 -C 10 cyclic structure together with the two adjacent carbon atoms in the imidazoline or imidazolidine ring.
6. The catalyst according to claim 2 , in which:
X 1 , X 2 are different and represent hydride or halide,
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 , and P(benzyl) 3 .
7. 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-1) or (Ib-1)
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 , and P(benzyl) 3 .
8. 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 (Ic) or (Id) in which
n is identical or different and represents an integer of 1 to 20,
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 electron donor selected from the group consisting of —O—, —S—, —Se—, —N(R)—, —P(R)—, —As(R)—, —S(═O)—, —PR 3 (═S)—, —PR 3 (═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,
with the remainder ligand(s) of L 1 , L 2 , and L 3 being a ligand/ligands different therefrom.
9. The catalyst according to claim 2 , in which:
X 1 , X 2 are identical or different and represent hydride, halide, in particular fluoride, chloride, bromide or iodide, 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 (Ic) or (Id) in which
n is identical or different and represents an integer of 1 to 5,
R is identical or different and represents C 1 -C 10 alkyl or C 6 -C 24 aryl, and
E is identical or different and represents oxygen, or sulfur,
with the remainder ligand(s) of L 1 , L 2 , and L 3 being a ligand/ligands different therefrom, 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 , and P(benzyl) 3 .
10. The catalyst according to claim 9 , in which:
X 1 , X 2 are different and represent hydride or halide,
one ligand of L 1 , L 2 , and L 3 has the general structure according to formulae (Ic) or (Id) in which
n is identical or different and represents an integer of 1 to 5,
R is identical or different and represents C 1 -C 10 alkyl or C 6 -C 24 aryl,
E is identical or different and represents oxygen, sulfur,
with the remainder ligand(s) of L 1 , L 2 , and L 3 being a ligand/ligands different therefrom, 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 , and P(benzyl) 3 .
11. The catalyst according to claim 9 , 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 (Ic-1)
with the remainder ligand(s) of L 1 , L 2 , and L 3 being a ligand/ligands different therefrom, 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(CH 2 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(cyclchexyl) 3 , P(neopentyl) 3 , and P(benzyl) 3 .
12. A process for hydrogenating substrates possessing at least one carbon-carbon double bond, the process comprising subjecting the substrate possessing at least one carbon-carbon double bond to a hydrogenation reaction in the presence of the catalyst according to claim 1 or 2 .
13. The process according to claim 12 , wherein the substrate to be hydrogenated is selected from the group consisting of terminal olefins, internal olefins, cyclic olefins, conjugated olefins, any further olefins having at least one carbon-carbon double bond and additionally at least one further polar unsaturated double or triple bond, and polymers having carbon-carbon double bonds.
14. The process according to claim 12 , wherein the substrate is selected from the group consisting of hydrocarbon compounds with a terminal unsaturated carbon-carbon double bond having the general formula C n H 2n ; hydrocarbon compounds with an internal unsaturated carbon-carbon double bond having the general formula C n H 2n ; cyclic hydrocarbon compounds with an unsaturated carbon-carbon double bond having a general formula C n H 2n-2 ; hydrocarbon compounds with at least two conjugated unsaturated carbon-carbon double bonds; and olefins having a unsaturated carbon-carbon double bond in the presence of at least one other unsaturated polar bond.
15. The process according to claim 12 , wherein the substrate is a polymer having carbon-carbon double bonds, and the polymer comprises repeating units based on at least one conjugated diene monomer.
16. The process according to claim 15 , wherein the substrate is a nitrile rubber comprising repeating units of at least one conjugated diene, at least one α,β-unsaturated nitrile and, if appropriate, one or more further copolymerizable monomers.
17. The process according to claim 14 , wherein:
the hydrocarbon compound with a terminal unsaturated carbon-carbon double bond having the general formula C n H 2n comprises a straight-chain or a branched hydrocarbon compound of any length;
the hydrocarbon compounds with an internal unsaturated carbon-carbon double bond having the general formula C n H 2n comprises a straight-chain or branched hydrocarbon compound of any length;
the cyclic hydrocarbon compounds with an unsaturated carbon-carbon double bond having a general formula C n H 2n-2 comprises cyclohexene;
the hydrocarbon compounds with at least two conjugated unsaturated carbon-carbon double bonds comprises a straight-chain or a branched hydrocarbon compound with at least two conjugated unsaturated double bonds; and
the olefins having a unsaturated carbon-carbon double bond in the presence of at least one other unsaturated polar bond comprise olefins with at least one terminal, internal, cyclic or conjugated carbon-carbon double bond and at least one further unsaturated polar bond selected from carbon-nitrogen, carbon-phosphorus, carbon-oxygen, and carbon-sulfur unsaturated polar bonds.
18. The process according to claim 16 , wherein the substrate is a nitrite rubber comprising repeating units of at least one conjugated diene selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene and mixtures thereof, of at least one α,β-unsaturated nitrite selected from the group consisting of acrylonitrile, methacrylonitrile, ethactylonitnle and mixtures thereof, and optionally of one or more further copolymerizable monomers selected from the group consisting of α,β-unsaturated monocarboxylic, dicarboxylic adds, their esters or amides.
19. A ruthenium-based complex catalyst according to formula (I)
wherein:
X 1 , X 2 are identical or different and represent hydride, halide, pseudohalide, alkoxide, amide, tosylate, trifiate, phosphate, borate, carboxylate, acetate, halogenated acetate, halogenated aikylsulfonate, or a weakly coordinating anion,
X 3 represents a non-coordinating anion,
t is either 0 or 1,
t′ is either 0 or 1,
u is either 0 or 1, wherein u and t may not both represent 0 at the same time, and
L 1 , L 2 , L 3 represent identical or different ligands, wherein one ligand of L 1 , L 2 , and L 3 has the general structure according to formulae (Ic) or (Id)
in which
n is identical or different and represents an integer of 1 to 5,
R is identical or different and represents C 1 -C 10 alkyl or C 6 -C 24 aryl, and
E is identical or different and represents oxygen, or sulfur,
with the remainder ligand(s) of L 1 , L 2 , and (if u=1) L 3 being a ligand/ligands different therefrom, 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 , and P(benzyl) 3 .