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.