The reaction of three equivalents of LiCH(SiMe) with TiCl(NMe) afforded the rare homoleptic Ti(III) alkyl Ti{CH(SiMe)} (1) which crystallized as blue needles in 32 % yield. Single crystal X-Ray data for 1 showed a trigonal pyramidal coordination geometry around titanium, which could be ascribed to weak interactions between the C-H bonds and the Ti(III) atom based on computational results. X-band EPR spectroscopy gives spectral parameters consistent with the proposed Ti(III) formulation. Solutions of 1 are unstable at room temperature owing to intramolecular C-H activation that gave a dimeric Ti(IV) complex [{(MeSi)HC}Ti{μ-CHSiMeCHSiMe}] (2).
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