Characterization of the Titanium(III) Tris(alkyl) Ti{CH(SiMe3)2}3 and its Conversion to a Dimeric Alkyl‐bridged Titanium(IV) Species

The reaction of three equivalents of LiCH(SiMe3)2 with TiCl3(NMe3)2 afforded the rare homoleptic Ti(III) alkyl Ti{CH(SiMe3)2}3 (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 give 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 [{(Me3Si)2HC}Ti{μ‐CH HSiMe3}]2 (2).