Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium tert-Butoxy Halides, Cp(x)TiX(y)(O(t)Bu)(4–(x+y)) (x, y = 1, 2; X = Cl, Br)

[Image: see text] Titanium tert-butoxy halides of the formula Cp(x)TiX(y)(O(t)Bu)(4–(x+y)) (x, y = 1, 2; X = Cl, Br) have been prepared thorough milling the reagents without solvent. In the case of the chloride derivatives, Cp(2)TiCl(2) is used as a starting material; in the case of the bromides, a mixture of LiCp, TiBr(4), and Li[O(t)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 Cp(2)TiCl(O(t)Bu), Cp(2)TiBr(O(t)Bu), and CpTiBr(2)(O(t)Bu), as well as for Cp(2)TiCl(O(i)Pr) and a redetermination of Cp(2)TiCl(OMe). The tert-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.