Titanium reduction in a soluble ziegler—natta catalyst

The spontaneous reduction of Ti^IV to Ti^III in soluble Ziegler—Natta catalysts of type Cp₂RTiCl·R’AlCl₂ (Cp = h⁵ -cyclopentadienyl, R and R’ = methyl or ethyl) was studied both spectrally and chromatographically. Varied were R, R’, Al/Ti ratio, total concentration, solvent, and added olefin. Kinetic order in Ti] could be varied from zero to second order by changing solvent. This can be explained by a mechanism in which a Cp₂ RTiCl—R’AlCl₂—olefin complex forms in the rate determining step and ligand R is expelled as half alkane half olefin. The expelled olefin may either polymerize or catalyze reduction by forming the rate-determining complex. Different apparent kinetic orders arise from differences in the olefin competitive reactions. The reaction products appear to form in a rapid bimolecular reaction following the rate-determining step. Evidence is presented that neither free radicals nor Cp₂RR’Ti are reduction intermediates. The intermediate is postulated to be a Ti^IV transient hydride formed by a reverse insertion step.