# US 5,703,257 A · Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides

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- Number: US 5,703,257 A
- Document ID: US5703257A
- Status: Granted
- Kind: A
- Application number: 08/469,185
- Filed: 1995-06-06
- Granted: 1997-12-30
- Earliest claimed: 1994-01-25
- Assignees: The Dow Chemical Company
- Inventors: Robert K. Rosen; Brian W.S. Kolthammer
- Web page: https://patentgrep.com/patent/US5703257A

## CPC

- C07F 17/00: Metallocenes
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- Y10S 526/943: Polymerization with metallocene catalysts
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A process for preparing bridged mono- and bis(cyclopentadienyl) metal dihydrocarbyloxy coordination complexes (I) by contacting in the presence of an aprotic organic diluent a metal compound of the formula M(OR).sub.4 with a dianionic salt compound. A process for preparing bridged mono- and bis(cyclopentadienyl) dihydrocarbyl metal coordination complexes (II) by contacting a complex (I) with a hydrocarbylation agent. A process for preparing bridged mono- and bis(cyclopentadienyl) metal dihalide coordination complexes (III) by contacting a complex (I) with a halogenation agent.

## Claims

### Claim 1

A process for preparing a metal dihydrocarbyl coordination complex corresponding to the formula: ##STR16## wherein: M is titanium;
Cp* is a cyclopentadienyl group bound in an .eta..sup.5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bound in an .eta..sup.5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and
R"' independently each occurrence is a hydrocarbyl group;
the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula: ##STR17## wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as defined for formula (II);
with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"', to form the metal dihydrocarbyl coordination complex of formula (II).

### Claim 2 (depends on 1)

A process according to claim 1 wherein a metal dihydrocarbyl coordination complex corresponding to the formula: ##STR18## wherein: R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
m is 1 or 2;
M is titanium; and
R"' is as defined for Formula II in claim 1;
is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: ##STR19## wherein: M, R', E, and m are as previously defined for Formula (IIa), and
R is as defined for Formula (I) in claim 1;
with the hydrocarbylation agent.

### Claim 3 (depends on 1)

A process according to claim 1 wherein a metal dihydrocarbyl coordination complex corresponding to the formula: ##STR20## wherein: R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms or two R' groups together form a divalent derivative thereof;
E is silicon or carbon;
R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms;
m is 1 to 8;
M is titanium; and
R"' is as defined for Formula II in claim 1;
is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: ##STR21## wherein R', E, R", M, and m are as defined for Formula (IIb), and
R is as defined for Formula (I) in claim 1;
with the hydrocarbylation agent.

### Claim 4 (depends on 1)

A process according to claim 1 wherein the metal coordination complex corresponding to formula (I) is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR).sub.4 wherein M is titanium and R is as defined for formula (I) in claim 1 with a dianionic salt compound corresponding to the formula:
(L.sup.+x).sub.y (Cp*--Z--Y).sup.-2 or ((LX).sup.+x).sub.y (Cp*--Z--Y).sup.-2
wherein:
L is a metal of Group 1 or 2 of the Periodic Table of the Elements,
X independently is chloro, bromo, or iodo,
x and y are either 1 or 2 and the product of x
and y equals 2, and
Cp*, Z, and Y are as defined for formula (II) in claim 1;
optionally followed by recovering the complex corresponding to formula (I).

### Claim 5 (depends on 1)

A process according to claim 1 wherein R each occurrence is independently selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl groups.

### Claim 6 (depends on 5)

A process according to claim 5 wherein R each occurrence is independently selected from the group consisting of alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms.

### Claim 7 (depends on 6)

A process according to claim 6 wherein R each occurrence is independently selected from the group consisting of isopropyl, n-butyl, and t-butyl.

### Claim 8 (depends on 1)

A process according to claim 1 wherein R"' is selected from the group consisting of alkyl, aryl, and aralkyl groups.

### Claim 9 (depends on 8)

A process according to claim 8 wherein R"' is a methyl, benzyl, or neopentyl group.

### Claim 10 (depends on 1)

A process according to claim 1 wherein the hydrocarbylation agent is selected from the group consisting of R"'Li, R"'.sub.2 Mg, R"'MgCl, R"'.sub.3 Al, and R"'-substituted aluminoxanes.

### Claim 11 (depends on 1)

A process according to claim 1 wherein the hydrocarbylation agent is R"'Li or R"'.sub.3 Al.

### Claim 12 (depends on 11)

A process according to claim 11 wherein the hydrocarbylation agent is trimethylaluminum.

### Claim 13 (depends on 1)

A process according to claim 1 wherein the aprotic organic diluent is a hydrocarbon or an ether.

### Claim 14 (depends on 13)

A process according to claim 13 wherein the hydrocarbon comprises an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms.

### Claim 15 (depends on 1)

A process according to claim 1 wherein the process is conducted at a temperature between 0.degree. and 100.degree. C.