Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium -Butoxy Halides, Cp TiX (O Bu) (, = 1, 2; X = Cl, Br).

Titanium -butoxy halides of the formula Cp TiX (O Bu) (, = 1, 2; X = Cl, Br) have been prepared thorough milling the reagents without solvent. In the case of the chloride derivatives, CpTiCl is used as a starting material; in the case of the bromides, a mixture of LiCp, TiBr, and Li[O Bu] is used. The stoichiometric ratios of the starting materials are reflected in the major products of the reactions. Single-crystal X-ray structures are reported for CpTiCl(O Bu), CpTiBr(O Bu), and CpTiBr(O Bu), as well as for CpTiCl(O Pr) and a redetermination of CpTiCl(OMe). The -butoxy derivatives are notable for their nearly linear Ti-O-C angles (>170°) that reflect Ti-O π-bonding, an interpretation supported with density functional theory calculations.