Unexpected cyclopentadienyl/alkoxo ligand exchange in titano- and zirconocene. New opportunities.

A simple new route to access heterometallic alkoxo precursors for a wide range of materials is reported. This unique synthetic method comprises elimination of the cyclopentadienyl ring from Cp2MCl2 (M = Ti, Zr) as CpH in the presence of M'(OR)2 (M' = Ca, Mn; OR = OCH2CH2OCH3 or OEt) in an alcohol as a source of protons. In one-pot reactions, we have prepared four different compounds with Ti2Ca4(mu6-O), Cp2Zr2Ca4(mu4-Cl), Zr10Mn10(mu3-O) 14, and Cp3Ti2(mu-OEt)2 motifs. The compounds were characterized by single-crystal X-ray structural analysis and NMR spectroscopy.