US 5,861,522 A · Production of bridged metallocene complexes and intermediates therefor

Abstract

Bridged metallocene compounds are produced by a process of promising commercial utility for plant-sized operations. One of the key steps of the process involves converting a deprotonated silicon-, germanium- or tin-containing ligand into the metallocene. Preferably, and in accordance with an embodiment of the invention, this is accomplished to great advantage by adding a diamine adduct of a Group IV, V, or VI metal tetrahalide to a solution or slurry formed from a deprotonated silicon-, germanium- or tin-containing ligand and an organic liquid medium so as to form a metallocene. The overall process of the invention involves the direct conversion of benzoindanones to benzoindanols which, without isolation, are converted to benzoindenes. Thereupon the benzoindenes are bridged by deprotonating the benzoindenes with a strong base such as butyllithium and reacting the resultant deprotonated product with a suitable silicon-, germanium- or tin-containing bridging reactant such as dichlorodimethylsilane. The resultant bridged product is deprotonated with a strong base such as butyllithium and reacted with a suitable Group IV, V, or VI metal-containing reactant such as ZrCl.sub.4 to provide a silicon-, germanium- or tin-bridged Group IV, V, or VI metal complex, such as a dihydrocarbylsilyl-bridged zirconocene complex.

Claims30

Dependent claims

A process for preparing a metallocene which comprises adding a diamine adduct of a Group IV, V, or VI metal tetrahalide to:

(a) a solution or slurry formed from a deprotonated silicon-, germanium- or tin-containing ligand and an organic liquid medium;
and/or
(b) a solution or slurry in an organic liquid medium in which a deprotonated silicon-, germanium- or tin-containing ligand is formed;
and/or
(3) an organic liquid medium containing a solution or slurry of said deprotonated silicon-, germanium- or tin-containing complex in whatever chemical form it exists while in said solution or slurry;
so as to form a metallocene.

3 more elements

A process which comprises:

1) mixing together at least one of each of the following:
(a) a 4,5-benzoindanone, (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, and (c) a hydroxyl-containing compound capable of interacting with (b) to serve as a hydrogen source, under reaction conditions causing a 4,5-benzoindanol to be formed;
2) catalytically dehydrating said 4,5-benzoindanol using a arylsulfonic acid catalyst to thereby form a 4,5-benzoindene;
3) deprotonating said 4,5-benzoindene with a strong base and reacting the resultant deprotonated intermediate with a reactant which in its original condition can be depicted by the formula R.sup.11 R.sup.12 M.sup.1 X.sub.2 where R.sup.11 and R.sup.12 are the same or different and each is (i) a hydrocarbyl group containing up to about 18 carbon atoms or (ii) a hydrocarbyl(oxyalkylene) or hydrocarbylpoly(oxyalkylene) group containing up to about 100 carbon atoms;
M.sup.1 is a silicon, germanium or tin atom;
and X is a halogen atom;
such that a silicon-, germanium- or tin-bridged complex of the 4,5-benzoindene is formed;
and
4) deprotonating said bridged complex with a strong base and adding a diamine adduct of a Group IV, V, or VI metal tetrahalide to:
(A) a solution or slurry formed from said deprotonated silicon-, germanium- or tin-bridged complex and an organic liquid medium;
and/or
(B) a solution or slurry in an organic liquid medium in which said deprotonated silicon-, germanium- or tin-bridged complex is formed;
and/or
(C) an organic liquid medium containing a solution or slurry of said deprotonated silicon-, germanium- or tin-bridged complex in whatever chemical form it exists while in said solution or slurry;
so as to form a silicon-, germanium- or tin-bridged Group IV, V, or VI metal-containing metallocene.

12 more elements

A process which comprises (a) deprotonating a 4,5-benzoindene with a strong base and reacting the resultant deprotonated intermediate while dissolved in a liquid lower dialkyl ether with a reactant which in its original condition can be depicted by the formula R.sup.11 R.sup.12 M.sup.1 X.sub.2 where R.sup.11 and R.sup.12 are the same or different and each is (i) a hydrocarbyl group containing up to about 18 carbon atoms or (ii) a hydrocarbyl(oxyalkylene) or hydrocarbylpoly(oxyalkylene) group containing up to about 100 carbon atoms;

M.sup.1 is a silicon, germanium or tin atom;
and X is a halogen atom;
such that a slurry of a silicon-, germanium- or tin-bridged complex of the 4,5-benzoindene is formed:
(b) separating the solids from the liquid phase;
and (c) adding a diamine adduct of a Group IV, V, or VI metal tetrahalide to:
(1) a solution or slurry formed from said deprotonated silicon-, germanium- or tin-containing complex and an organic liquid medium;
and/or
(2) a solution or slurry in an organic liquid medium in which said deprotonated silicon-, germanium- or tin-containing complex is formed;
and/or
(3) an organic liquid medium containing a solution or slurry of said deprotonated silicon-, germanium- or tin-containing complex in whatever chemical form it exists while in said solution or slurry;
so as to form a silicon-, germanium- or tin-bridged Group IV, V, or VI metal-containing metallocene.

8 more elements

Dependencies are inferred from the claim text.

Production of bridged metallocene complexes and intermediates therefor

Life of this patent

Production of bridged metallocene complexes and intermediates therefor

Life of this patent

Abstract

Claims30