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(μ₆-O), Cp₂Zr₂Ca₄(μ₄-Cl), Zr₁₀Mn₁₀(μ₃-O)₁₄, and Cp₃Ti₂(μ-OEt)₂ motifs. The compounds were characterized by single-crystal X-ray structural analysis and NMR spectroscopy.