Synthesis of ANSA-metallocene catalysts

Claim 2

A process of synthesizing in high yield ansa-metallocene complexes of the formula: ##STR6## wherein Cp independently and in each occurrence is cyclopentadienyl, indenyl, or fluorenyl, or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said cyclopentadienyl, indenyl, fluorenyl or related group, X is a bridging group which links the Cp groups, M is a metal selected from the group consisting of Group 3, 4, and 5 metals, R and R' are the same or different and are each hydrogen or hydrocarbyl radicals of from C 1 to C 20 , or silyl radicals, and n is from 3 to 5, said process comprising: reacting an ansa-bis Cp compound of the formula HCp--X--CpH where Cp and X are as above defined with a metal amide complex to provide a high yield of ansa-metallocene complex.

Claim 3

The process of claim 1 wherein the Group 4 metal is selected from the group consisting of zirconium, titanium and hafnium.

Claim 4

The process of claim 2 wherein the metal is zirconium.

Claim 5

The process of claim 1 wherein R and R' are independently C 1 to C 4 alkyl.

Claim 6

The process of claim 4 wherein R and R' are methyl and the gaseous byproduct dimethylamine is not swept away from the reaction as it is produced.

Claim 7

The process of claim 1 wherein said process is conducted at a temperature ranging from 25° C. to 250° C.

Claim 8

The process of claim 1 wherein said process is conducted at a temperature ranging from 80° C. to 125° C.

Claim 9

The process of claim 1 wherein the reaction is conducted in the presence of a nonaqueous, nonalcoholic organic solvent.

Claim 10

The process of claim 8 wherein the solvent is selected from the group consisting of hydrocarbons, toluene, ethers, chlorinated hydrocarbons and tetrahydrofuran.

Claim 11

The process of claim 1 where X is ethylene and Cp is indenyl.

Claim 12

A process of synthesizing in high yield ansa-metallocene complexes of the formula: ##STR7## wherein Cp independently and in each occurrence is cyclopentadienyl, indenyl, or fluorenyl, or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said cyclopentadienyl indenyl, fluorenyl or related group, X is a bridging group which links the Cp groups, M is a metal selected from the group consisting of Group 3, 4, and 5 metals, R and R' are the same or different and are each hydrogen or hydrocarbyl radicals of from C 1 to C 20 , or silyl radicals, and n is from 3 to 5, said process comprising: reacting an ansa-bis Cp compound of the formula HCp--X--CpH where Cp and X are as above defined with a metal amide complex to provide a high yield of ansa-metallocene complex; and thereafter, isolating the ansa-metallocene complex from the reaction mixture.

Claim 13

A process of synthesizing in high yield ansa-metallocene complexes of the formula: ##STR7## wherein Cp independently and in each occurrence is cyclopentadienyl, indenyl, or fluorenyl, or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said cyclopentadienyl indenyl, fluorenyl or related group, X is a bridging group which links the Cp groups, M is a metal selected from the group consisting of Group 3, 4, and 5 metals, R and R' are the same or different and are each hydrogen or hydrocarbyl radicals of from C 1 to C 20 , or silyl radicals, and n is from 3 to 5, said process comprising: reacting an ansa-bis Cp compound of the formula HCp--X--CpH where Cp and X are as above defined with a metal amide complex to provide a high yield of ansa-metallocene complex; and thereafter, isolating the ansa-metallocene complex from the reaction mixture.

Claim 14

The process of claim 11 wherein the metal is a Group 4 metal and n is 4.

Claim 15

The process of claim 12 wherein the metal is zirconium and n is 4.

Claim 16

The process of claim 11 wherein R and R' are both methyl.

Claim 17

The process of claim 14 wherein X is an ethylene moiety and Cp is indenyl.

Claim 18

The process of claim 11 wherein R and R' are methyl and the gaseous byproduct dimethylamine is not swept away from the reaction as it is produced.

Claim 19

A process of synthesizing in high yield rac ansa-metallocene complexes of the formula: ##STR8## wherein Cp independently and in each occurrence is a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted cyclopentadienyl, an indenyl, a fluorenyl, or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said indenyl, fluorenyl, or related group, X is a bridging group which links the Cp groups, M is a metal selected from the group consisting of Group 3, 4, and 5 metals, R and R' are the same or different or linked and are each hydrogen or hydrocarbyl radicals of from C 1 to C 20 , or silyl radicals, and n is from 3 to 5, said process comprising: reacting a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted ansa-bis-cyclopentadiene, or an ansa-bis-indene, or an ansa-bis-fluorene or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said ansa-bis-indene, ansa-bis-fluorene or related group, with a metal amide complex to provide a high yield of rac ansa-metallocene complex.

Claim 20

A process of synthesizing in high yield rac ansa-metallocene complexes of the formula: ##STR8## wherein Cp independently and in each occurrence is a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted cyclopentadienyl, an indenyl, a fluorenyl, or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said indenyl, fluorenyl, or related group, X is a bridging group which links the Cp groups, M is a metal selected from the group consisting of Group 3, 4, and 5 metals, R and R' are the same or different or linked and are each hydrogen or hydrocarbyl radicals of from C 1 to C 20 , or silyl radicals, and n is from 3 to 5, said process comprising: reacting a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted ansa-bis-cyclopentadiene, or an ansa-bis-indene, or an ansa-bis-fluorene or a related group that can π-bond to the metal, or a hydrocarbyl, alkyl, aryl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid, or halohydrocarbylmetalloid substituted derivative of said ansa-bis-indene, ansa-bis-fluorene or related group, with a metal amide complex to provide a high yield of rac ansa-metallocene complex.

Claim 21

The process of claim 17 which includes as an additional step isolating the rac ansa-metallocene complex.

Claim 22

The process of claim 18 wherein X is ethylene and Cp is indenyl.

Claim 23

The process of claim 1 which includes a step of converting the ansa-metallocene amido complex to an ansa-metallocene chloride complex.