A Terminal and Four-Coordinate Titanium Alkylidene Prepared by Oxidatively Induced α-Hydrogen Abstraction

One-electron oxidation of the β-diketiminate titanium(III) bis-neopentyl complex (Nacnac)Ti(CH<sub>2</sub><i><sup>t</sup></i><sup></sup>Bu)<sub>2</sub> (Nacnac = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6-(CHMe<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) promotes α-abstraction to afford the rare and terminal four-coordinate neopentylidene (Nacnac)TiCH<i><sup>t</sup></i><sup></sup>Bu(OTf), which was structurally characterized. Alkylidene (Nacnac)TiCH<i><sup>t</sup></i><sup></sup>Bu(OTf) reacts cleanly with benzophenone and the imine functionality of the Nacnac ligand to afford the corresponding Wittig-type products.