Ruthenium-based complexes, their preparation and use as catalysts

Patent metadata

Field	Value
Publication number	US-9920086-B2
Application number	US-201414892451-A
Country	US
Kind code	B2
Filing date	May 20, 2014
Priority date	May 24, 2013
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

The present invention relates to novel Ruthenium-based complex compounds which represent viable catalysts, in particular for all sorts of metathesis reactions. Such complex compounds can be prepared by a novel, very favorable and cost efficient method which includes the introduction of an alkylidene ligand into the complex by using vinyl sulfides or vinyl ethers.

First claim

The invention claimed is:

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

wherein:
X 1 represents an anionic ligand;
Y is O or S;
R 1 is substituted or unsubstituted C 6 -C 14 -aryl, an N-heterocyclic carbene ligand or P(R′) 3 with R′ being identical or different and representing either substituted or unsubstituted, straight chain or branched C 1 -C 14 alkyl, substituted or unsubstituted C 6 -C 24 aryl, or substituted or unsubstituted C 3 -C 20 cycloalkyl;
R represents substituted or unsubstituted, straight chain or branched C 1 -C 14 -alkyl;
L 2 represents 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 in the range of from 1 to 20,
D is identical or different and represents hydroxy, alkoxy, aryloxy, thiol, thiolate, thioether, selenol, selenoether, amine, phosphine, phosphate, phosphite, arsine, sulfoxide, sulfone, alkyl, 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 3 is identical or different and represents H, alkyl or aryl;
E is identical or different and represents a divalent moiety capable 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 capable of acting as a two electron donor; and
R 2 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 2 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; and

L 1 is an N-heterocyclic carbene ligand which is different from general structures (Ia*), (Ib*), (Ic*), and (Id*).

2. The ruthenium-based complex according to claim 1 , wherein X 1 is halide, pseudohalide, alkoxide, amide, triflate, phosphate, borate, carboxylate, acetate, halogenated acetate, halogenated alkylsulfonate, tosylate, any weakly coordinating anionic ligands, straight-chain or branched C 1 -C 30 -alkyl or C 6 -C 24 -aryl.

3. The ruthenium-based complex according to claim 1 , wherein L 1 represents an imidazoline or imidazolidine ligand having a structure corresponding to the general formulae (IIa), or (IIb),

wherein under the proviso that L 1 is different from the general formulae (Ia*), (Ib*), (Ic*) and (Id*),
R 4 , R 5 , R 6 , R 7 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 1 -C 20 -arylsulphonate or C 1 -C 20 -alkylsulphinyl
or in the alternative
R 6 and R 7 have the above mentioned meanings and at the same time R 4 and R 5 jointly form a C 6 -C 10 cyclic structure together with the two adjacent carbon atoms in the imidazoline or imidazolidine ring,
the meanings of the substituents R 4 , R 5 , R 6 , R 7 are either unsubstituted or substituted by one or more substituents.

4. The ruthenium-based complex according to claim 3 , wherein the imidazoline or imidazolidine ligand has the following structures (III-a) to (III-o), where Ph is in each case a phenyl substituent, Bu is any type of butyl substituent, Mes is in each case a 2,4,6-trimethylphenyl substituent and (iPr) 2 Ph is in all cases 2,6-diisopropylphenyl

5. The ruthenium-based complex according to claim 1 , wherein R 1 represents unsubstituted C 6 -C 14 -aryl or C 6 -C 14 -aryl being substituted with 1, 2, 3, 4, 5 or more substituents selected from the group consisting of F, Cl, Br, I, NO 2 , and CH 3 .

6. The ruthenium-based complex according to claim 1 , wherein R represents straight chain or branched, substituted or unsubstituted C 1 -C 8 -alkyl.

7. The ruthenium-based complex according to claim 1 , wherein:
X 1 represents halide, phosphate, borate, carboxylate, acetate, trifluoroacetate, trifluoromethylsulfonate or tosylate;
Y is O or S;
R 1 represents unsubstituted C 6 -C 14 -aryl or C 6 -C 14 -aryl being substituted with 1, 2, 3, 4, 5 or more substituents selected from the group consisting of F, Cl, Br, I, NO 2 , and CH 3 ;
R represents unsubstituted, straight chain or branched C 1 -C 5 -alkyl or a straight chain or branched C 1 -C 5 -alkyl which is substituted by C 6 -C 14 -aryl;
L 1 represents an imidazoline or imidazolidine ligand having a structure corresponding to the general formulae (IIa), or (IIb),

wherein under the proviso that L 1 is different from the general formulae (Ia*), (Ib*), (Ic*) and (Id*) as defined for L 2 ,
R 4 , R 5 , R 6 , R 7 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 6 , R 7 have the above mentioned meanings and at the same time R 4 and R 5 jointly form a C 6 -C 10 cyclic structure together with the two adjacent carbon atoms in the imidazoline or imidazolidine ring; and

L 2 represents either a ligand of the structure (Ia*) or (Ib*) in which
n is identical or different and represents an integer of 1 to 5, and
D is identical or different and represents C 1 -C 10 -alkoxy or C 6 -C 14 -aryloxy,
or
a ligand of the structure (Ic*) or (Id*) in which
n is identical or different and represents an integer of 1 to 5; and
E is identical or different and represents oxygen or sulfur; and
R 3 is identical or different and represents C 1 -C 10 alkyl or C 6 -C 14 aryl, wherein all aforementioned can be unsubstituted or substituted by one or more substituents,
with
R 2 being identical or different in a respective moiety (Ia*), (Ib*), (Ic*) or (Id*) and representing H, C 1 -C 10 -alkyl, C 6 -C 14 -aryl, halide, or in the alternative two R 2 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.

8. The ruthenium-based complex according to claim 1

Assignees

• Lanxess Deutschland Gmbh
• Governing Council Univ Toronto
• Arlanxeo De Gmbh

Inventors

• Stephan Douglas Wade
• Lund Clinton
• Sgro Michael
• Dahcheh Fatme
• Ong Christopher

Classifications

• C08C19/00

  Chemical modification of rubber · CPC title

• C08L9/02

  Copolymers with acrylonitrile · CPC title

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• B01J31/00

  Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002}) · CPC title

• C08F236/12

  with nitriles · CPC title