Preparation and characterization of alkane– and arene–chalcogenolate complexes of η5-cyclopentadienyltitanium(IV): first synthesis of [Ti(η5-C5H5)(SeCH3)3]

Abstract

A simple synthesis of [Ti(cp)Br₃](1)(cp =η⁵-C₅H₅) from [Ti(cp)Cl₃] and BBr₃ is described. Reaction of complex (1) with Na(SCH₃) or Li(SeR)(R = CH₃ or C₆H₅) afforded the derivatives [Ti(cp)(SCH₃)₃](2), [Ti(cp)(SeCH₃)₃](3), or [Ti(cp)(SeC₆H₅)₃](4), respectively. Complexes (2)–(4) were characterized by ¹H n.m.r., i.r., and mass spectroscopy; (3), the first example of a cyclopentadienyltris(selenolato)titanium compound, was also studied by ⁷⁷Se n.m.r. spectroscopy. The oxidation and hydrolysis behaviour of (2) and (3) in solution is discussed on the basis of their ¹H n.m.r. spectra.