C–H Activation on an Oxo-Bridged Dititanium Complex: From Alkyl to μ‑Alkylidene Functionalities

Thermal treatment of the dinuclear compound [{Ti­(η5-C5Me5)­(CH2SiMe3)2}2­(μ-O)] (1) provides the formation of the metallacycle derivatives [Ti25-C5Me5)2­(μ-CH2­SiMe2CH2)­(CH2­SiMe3)2­(μ-O)] (2) and [Ti25-C5Me5)2­(μ-CH2­SiMe2CH2)2­(μ-O)] (3) and the μ-alkylidene complex [Ti25-C5Me5)2­(μ-CH2­SiMe2CH2)­(μ-CHSiMe3)­(μ-O)] (4) by sequential carbon–hydrogen activation processes. The reaction of 3 with tert-butylisocyanide, in 1:1 and 1:2 ratios, leads to the η2-iminoacyl complexes [Ti25-C5Me5)2­(μ-tBuNC­CH2­SiMe2CH2)­(μ-CH2­SiMe2CH2)­(μ-O)] (5) and [Ti25-C5Me5)2­(μ-tBuNC­CH2­SiMe2CH2)2­(μ-O)] (6), respectively. The molecular structures of complexes 3, 4, 5, and 6 have been determined by single-crystal X-ray diffraction analyses.