A Bridging bis-Allyl Titanium Complex: Mechanistic Insights into the Electronic Structure and Reactivity

Treatment of the dinuclear compound [{Ti(η5-C5Me5)Cl2}2(μ-O)] with allylmagnesium chloride provides the formation of the allyltitanium(III) derivative [{Ti(η5-C5Me5)(μ-C3H5)}2(μ-O)] (1), structurally identified by single-crystal X-ray analysis. Density functional theory (DFT) calculations confirm that the electronic structure of 1 is a singlet state, and the molecular orbital analysis, along with the short Ti–Ti distance, reveal the presence of a metal–metal single bond between the two Ti(III) centers. Complex 1 reacts rapidly with organic azides, RN3 (R = Ph, SiMe3), to yield the allyl μ-imido derivatives [{Ti(η5-C5Me5)(CH2CH═CH2)2}2(μ-NR)(μ-O)] [R = Ph(2), SiMe3(3)] along with molecular nitrogen release. Reaction of 2 and 3 with H2 leads to the μ-imido propyl species [{Ti(η5-C5Me5)(CH2CH2CH3)2}2(μ-NR)(μ-O)] [R = Ph(4), SiMe3(5)]. Theoretical calculations were used to gain insight into the hydrogenation mechanism of complex 3 and rationalize the lower reactivity of 2. Initially, the μ-imido bridging grou...