Preparation of titanocenes

This application is a continuation-in-part of Blankenship application PCT/US96/18666 filed 22 Nov., 1996 and incorporated herein by reference.

This invention relates to the preparation of chiral titanocenes. More particularly, the invention relates to dialkylsilylbis(2-alkyl-4-arylindenyl) metallocenes.

U.S. Pat. No. 5,629,254 at column 29, line 5, et. seq., describes compounds of the Formula Ia:

in which R a may be a 1 to 20 carbon atom hydrocarbon group, (R b ) may be a 6 to 16 carbon atom aryl group, M may be titanium, zirconium or hafnium. X 1 and X 2 may be a halogen atom and Y 1 may be a divalent-silicon containing group.

There may also be used the transition metal compounds obtained by substituting titanium metal of hafnium metal . . . for zirconium metal in the above-exemplified compounds. [Col. 32, 11. 5-9]

It appears that the sole reference to a method which may be useful for preparing the Formula Ia compounds is found at column 13, lines 21-25 of U.S. Pat. No. 5,629,254 which states:

The transition metal compounds according to the present invention can be prepared in accordance with the methods described in Journal of Organometallic Chem. 288 (1985), pages 63 to 67, European Patent Publication No. 0,320,762 specification and Examples thereof . . . .

Neither reference specifically exemplifies the synthesis of any titanocene. Nor does any working example of U.S. Pat. No. 5,629,254 do so.

This invention provides a method for preparing the titanocene compounds of Formula Ia.

In a first step, a 2-alkyl-4-aryl indene is converted to a dialkali metal salt, preferably a dilithium salt.

The dialkali metal salt is then reacted in a second step with a dihalodialkyl silane to produce a bis-indenyl compound of Formula II:

in which R a and R b are as described with respect to Formula Ia and in which R c is a one to ten carbon atom alkyl group.

In a third step, the Formula II compound is combined with a titanium trichloride (TiCl 3 ) containing mixture formed by reacting titanium tetrachloride (TiCl 4 ) with an alkali metal alkyl compound, wherein a metallocene ligand is produced in which titanium is present in a plus three oxidation state. The titanium is oxidized to the plus four state, for example, by reaction with cuprous chloride or chloroform, wherein a reaction mixture which contains contain the desired titanocene of Formula III is produced.

FIG. 1 is a proton nuclear magnetic resonance (NMR) spectrum of rac-dimethylsilyl(2-methyl-4-phenyl indenyl) titanium dichloride acquired with a JEOL Eclipse 400 NMR spectrometer prepared by the method of the sample labelled 552-001(c).3.

A typical Formula Ia titanocene synthesis includes a first step in which a 2-alkyl-4-aryl indene having the Formula IV:

in which R a and R b are as previously described and which is reacted in a first reaction vessel with an alkali metal alkyl compound having the formula RM in which R is a straight or branched chain 2 to 10 carbon atom alkyl group and M is sodium, potassium or, preferably, lithium to provide a first reaction mixture which contains a dialkali metal salt of the Formula II compound. The reactants are combined in substantially stoichiometric amounts in a non-interfering, preferably hydrocarbon, medium.

Useful hydrocarbon media include aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene and xylene. Toluene is preferred.

In a second step, titanium tetrachloride in a second reaction vessel is reacted as in the first step in a non-interfering, preferably hydrocarbon medium as in the first step with an alkali metal alkyl compound RM to produce a second reaction mixture containing titanium trichloride.

The titanium trichloride containing mixtures are produced by the preferably stoichiometric (1:1) reaction of an organometallic compounds, such as n-butyl lithium or n-butyl magnesium chloride, with titanium tetrachloride in the non-interfering solvent medium. These mixtures are used directly without isolation of the titanium trichloride.

In a third step the first and second reaction mixtures are combined, for example, in the second reaction vessel for reaction to produce a titanocene catalyst ligand in which titanium is present in a plus three oxidation state. An oxidizing agent, e.g., cuprous chloride or chloroform, is added with agitation to produce a third reaction mixture in which the desired titanocene of Formula III is present as a mixture of rac solid and meso isomers.

The isomer mixture is separated from the reaction mixture and dried. The dry mixture of rac and meso isomers is resolved, for example, by treatment with a selective solvent preferably for the meso isomer to provide the rac isomer in substantially pure form. The isomer mixture may also be resolved by the method described in Gately application entitled “Preparation and Separation of Rac and Meso Compound Mixtures” filed Jun. 9, 1997.