NOVEL BENT-SANDWICH TITANIUM(III) AND TITANIUM(IV) ORGANOMETALLICS

The reaction between closo-exo-Li-1-Li-2,3-(SiMe(3))(2)-2,3-C2B4H4 (1) and anhydrous Cp(2)TiCl(2), in a molar ratio of 1:1, in. a 1:1 mixtur e of dry benzene and n-hexane produced, in. 60% yield, [commo-1-Cp-1-T i-2,3-(SiMe(3))(2)-2,3-C2B4H4](2) (2), the first example of a paramagn etic Ti(III) d(1)-d(1) dimer not having distinct bridging ligands. Che mical oxidation of 2 with anhydrous TiCl4 in, a 1:1 molar ratio in THF produces, in 86% yield a previously unknown. diamagnetic (d(0)) Ti(IV ) complex, o-1-Cp-1-Cl-1-THF-1-Ti-2,3-(SiMe(3))(2)-2,3-C2B4H4 (3), who se crystal structure shows a distorted tetrahedral environment about t he metal center similar to those of titanocene derivatives.