Bimetallic complex comprising cyclopentadienyl and amidine ligands
View Patent ↗The present invention relates to a new bimetallic complex of the formula (1) wherein: M is a group 4-6 metal R 1 means is a substituent comprising a heteroatom of group 15, through which R 1 is bonded to the imine carbon atom; R 2 -R 6 are the same or different and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R 2 -R 6 may be linked to each other to form a ring; R 7 -R 10 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R 7 -R 10 may be linked to each other to form a ring; L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and X is an anionic ligand, and r is an integer denoting the number of anionic ligands X and wherein the two cyclopentadienyl-amidinato-metal-containing moieties as in the brackets are the same or different.
1. A bimetallic complex of the formula (1)
having two cyclopentadienyl-amidinato-metal-containing moieties as in the brackets,
wherein:
M is a group 4-6 metal;
R 1 is a substituent comprising nitrogen, through which R 1 is bonded to the imine carbon atom;
R 2 -R 6 are the same or different, and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group, or the adjacent R 2 -R 6 are optionally linked to each other to form a ring;
R 7 -R 10 are the same or different, and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group, or the adjacent R 7 -R 10 are optionally linked to each other to form a ring;
L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and
X is an anionic ligand, and r is an integer denoting the number of anionic ligands X, and
wherein the two cyclopentadienyl-amidinato-metal-containing moieties are the same or different.
2. The bimetallic complex according to claim 1 , wherein M is selected from the group consisting of Ti, Zr and Hf.
3. The bimetallic complex according to claim 1 , wherein R 2 -R 6 are the same or different and each represents a hydrogen atom or a C1-5 alkyl group.
4. The bimetallic complex according to the claim 1 , wherein each X independently represents a halogen atom, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group or a C1-20 hydrocarbon-substituted amino.
5. The bimetallic complex according to claim 1 , wherein j is zero.
6. The bimetallic complex according to claim 1 , wherein R 7 -R 10 are each a hydrogen atom.
7. A process for producing the bimetallic complex represented by the formula (1) according to claim 1 , the process comprising:
reacting a ligand compound of the formula (2)
wherein R 1 and R 7 -R 10 have the same meaning as given in claim 1 , with a metal compound represented by the formula (3)
wherein M, R 2 -R 6 , X, L and r and j have also the same meaning as given in claim 1 .
8. A catalyst system comprising
a) a metal complex of the formula (1) according to claim 1 , and
b) an activator.
9. The catalyst system according to claim 8 , further comprising a scavenger c), wherein the scavenger c) is hydrocarbyl of a metal or metalloid of group 1-13 or its reaction products with at least one sterically hindered compound containing a group 15 or 16 atom.
10. The catalyst system according to claim 8 , wherein the activator b) is a borane, a borate, or an organoaluminum compound.
11. A process for the preparation of a polymer by polymerizing at least one olefinic monomer, the process comprising contacting at least one olefinic monomer with the catalyst system according to claim 8 .
12. The process according to claim 11 , wherein the at least one olefinic monomer comprises ethylene and at least a C 3 -C 12 -α-olefin.
13. The process according to claim 11 , wherein the at least one olefinic monomer comprises ethylene, at least one C 3-12 alpha olefin, and at least one non-conjugated diene.
14. The process according to claim 13 , wherein the at least one non-conjugated diene is selected from the group consisting of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornadiene, dicyclopentadiene, and vinylcyclohexene.
15. The bimetallic complex according to claim 1 , wherein:
M is selected from the group consisting of Ti, Zr and Hf;
R 2 -R 6 are the same or different and each represents a hydrogen atom or a C1-5 alkyl group;
each X independently represents a halogen atom, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group, or a C1-20 hydrocarbon-substituted amino;
j is zero; and
R 7 -R 10 are each a hydrogen atom.
16. The bimetallic complex according to claim 1 , wherein:
M is Ti;
R 2 -R 6 are methyl;
each X independently is Cl or methyl;
j is zero; and
R 7 -R 10 are each a hydrogen atom.
17. A bimetallic complex of the formula (1)
having two identical, or two different moieties as in the brackets,
wherein:
M is a group 4-6 metal;
R 1 is a substituent comprising a heteroatom of group 15, through which R 1 is bonded to the imine carbon atom;
R 2 -R 6 are the same or different and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon groups), a C1-20 hydrocarbon-substituted amino group or the adjacent R 2 -R 6 may be linked to each other to form a ring;
R 7 -R 10 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R 7 -R 10 may be linked to each other to form a ring;
L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and
X is an anionic ligand, and r is an integer denoting the number of anionic ligands X.