IN-SITU GENERATION OF RUTHENIUM CATALYSTS FOR OLEFIN METATHESIS
The present invention relates to a process for preparing olefins by means of metathesis, which comprises the following steps a. provision of an olefin reaction mixture containing at least one olefin, b. addition of a ruthenium compound of the general formula [RuX 2 L 1 x L 2 y ] z (I), where X=anionic ligand; L 1 =uncharged π-bonding ligand; L 2 =uncharged electron donor ligand; x=0, 1; y=1, 2, 3; z=1, 2, c. addition of a Lewis acid and/or an anionic, noncoordinating salt, d. reaction at temperatures in the range from 30° C. to 140° C., where no addition of an alkyne or alkynol is carried out. The invention further relates to the use of this process in metathesis reactions.
1 . A process for preparing olefins by means of metathesis comprising the following steps
a. providing an olefin reaction mixture comprising at least one olefin,
b. adding a ruthenium compound of the general formula [RuX 2 L 1 x L 2 y ] z (I), where X is an anionic ligand; L 1 is an uncharged π-bonding ligand; L 2 is an uncharged electron donor ligand; x=0 or 1; y=1, 2, or 3; z=1 or 2,
c. adding a Lewis acid or adding a Lewis acid and an anionic, noncoordinating salt,
d. reacting at temperatures in the range from 30° C. to 140° C.,
wherein no addition of an alkyne or alkynol is carried out.
2 . The process according to claim 1 , wherein the anionic ligands X are identical and are each chlorine and L 2 is selected from the group consisting of nitrogen bases, phosphanes, phosphinites, phosphonites, phosphites and arsanes.
3 . The process according to claim 2 , wherein L 1 is selected from the group consisting of benzene, toluene, xylene, cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetrahydronaphthalene and naphthalene, and L 2 is selected from the group consisting of N-heterocyclic carbenes and phosphanes.
4 . The process according to claim 3 , wherein L 2 is selected from the group consisting of P(phenyl) 3 , P(cyclohexyl) 3 and N-heterocyclic carbenes of the formula VI, VII, VIII, IX, X and XI.
5 . The process according to claim 1 , wherein the ruthenium compound is selected from the group consisting of (a) compounds derived from formula (I) wherein x=1, y=1, z=1 (formula II), (b) compounds derived from formula (I) wherein x=0, y=2, z=1 (formula III) and (c) compounds derived from formula (I) wherein x=0, y=1, z=2 (formula IV)
6 . The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula RuX 2 L 1 L 2 (II), wherein the anionic ligands X are identical and are each chlorine and L 2 is selected from the group consisting of N-heterocyclic carbenes and phosphanes.
7 . The process according to claim 6 , wherein L 1 is selected from the group consisting of benzene, toluene, xylene, cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetrahydronaphthalene and naphthalene, and L 2 is selected from the group consisting of P(cyclohexyl) 3 and the N-heterocyclic carbenes of the formulae VI, VII, VIII, IX, X and XI.
8 . The process according to claim 7 , wherein the ruthenium compound is selected from the group consisting of compounds of the formulae A, B and C.
9 . The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula RuX 2 L 2 2 (III), wherein the anionic ligands X are identical and are each chlorine and each of the ligands L 2 are selected independently from the group consisting of N-heterocyclic carbenes and phosphanes.
10 . The process according to claim 9 , wherein each of the ligands L 2 are selected independently from the group consisting of P(cyclohexyl) 3 , P(phenyl) 3 and the N-heterocyclic carbenes of the formulae VI, VII, VIII, IX, X and XI.
11 . The process according to claim 10 , wherein one L 2 is selected from the group consisting of P(cyclohexyl) 3 and P(phenyl) 3 and the other L 2 is selected from the group consisting of the N-heterocyclic carbenes of the formulae VI, VII, VIII, IX, X and XI.
12 . The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula [RuX 2 L 2 ] 2 (IV), where the anionic ligands X are identical and are each chlorine and each of the ligands L 2 are selected independently from the group consisting of N-heterocyclic carbenes and phosphanes.
13 . The process according to claim 12 , wherein the ligands L 2 are identical and are selected from the group consisting of P(cyclohexyl) 3 and the N-heterocyclic carbenes of the formulae VI, VII, VIII, IX, X and XI.
14 . The process according to claim 1 , wherein the anionic, noncoordinating salt is selected from the group consisting of a sodium, potassium, caesium, barium, calcium or magnesium salt of PF 6 − , BF 4 − , BH 4 − , F 3 CSO 3 − , H 3 CSO 3 − , ClO 4 − , SO 4 2− , HSO 4 − , NO 3 − , PO 4 3− , HPO 4 2− , H 2 PO 4 − , CF 3 COO − , B(C 6 F 5 ) 4 − , B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 − , RSO 3 − and R′COO − , wherein each of R and R′ are selected independently from the group consisting of (C 1 -C 20 )-alkyl and (C 6 -C 14 )-aryl.
15 . The process according to claim 1 , wherein the Lewis acid is selected from the group consisting of aluminium, boron, chromium, cobalt, iron, copper, magnesium, lanthanum, manganese, nickel, palladium and zinc salts of Cl − , Br − , I − , PF 6 − , BF 4 − , CF 3 COO − , B(C 6 F 5 ) 4 − , B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 − , R x COO − , (R y COCHCOR z ) − , wherein each of R x , R y , and R z are selected independently from the group consisting of (C 1 -C 20 )-alkyl and (C 6 -C 14 )-aryl.
16 . The process according to claim 1 , wherein step c) further comprises adding a halogen compound.
17 . The process according to claim 16 , wherein the halogen compound is selected from the group consisting of potassium iodide, potassium bromide, tetrabutylammonium bromide, 1,2-dibromocyclohexane, 1,2-bromocyclohexane, 1,2-dibromoethane, 1,2-dibromo-4,5-dimethylbenzene, 1,2-diiodobenzene, 1-bromo-2-iodobenzene, 2-bromostyrene, (2-bromoethyl)benzene and (3-bromopropyl)benzene.
18 . The process according to claim 1 , wherein a ratio of the ruthenium compound to the at least one olefin is in the range from 1:10 to 1:1 000 000.
19 . The process according to claim 1 , wherein a ratio of the ruthenium compound to the anionic, noncoordinating salt is in the range from 1:1 to 1:10.
20 . The process according to claim 1 , wherein a ratio of the ruthenium compound to the Lewis acid is in the range from 1:1 to 1:10.
21 . The process according to claim 16 , wherein a ratio of the ruthenium compound to the halogen compound is in the range from 1:1 to 1:333.
22 . Use of the process according to claim 1 , wherein the process is used in metathesis reactions selected from the group consisting of cross-metathesis (CM), ring-closing metathesis (RCM), ring-opening metathesis (ROM), ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET).