Reactivity of new azido-complexes of titanium and vanadium

Abstract

Mono- and bis-azido-complexes of Ti^IV and V^V have been prepared in good yield from chloro- or alkoxo-derivatives of the transition metal, using SiMe₃(N₃) as azide source. The stable azides [Ti(η-C₅H₅)Cl₂(N₃)], [Ti(OPrⁱ)₂(N₃)₂], [TiCl(OPrⁱ)₂(N₃)], [VO(OPrⁱ)(N₃)₂], and [VO(OCH₂Bu^t)(N₃)₂] have been isolated and characterized. The azido-group can be displaced by reaction with protic reagents and HN₃ is eliminated. The compounds also react with phosphines to form phosphiniminato-complexes, with N₂ elimination.