Reaction of <i>p</i>-Toluenesulfonylamide and M(NMe₂)₄ (M = Ti, V): Generation of Electron-Deficient Imido Complexes of Early Transition Metals

p-Toluenesulfonamide (p-TsNH2) was succesfully employed as an imido ligand precursor in the synthesis of highly air- and moisture-sensitive titanium(IV) and vanadium(IV) complexes. Reaction of M(NMe2)4 (M = Ti, V) with TsNH2 in toluene afforded [M(μ-NTs)(NMe2)2]2 dimer complexes (M = Ti (1), V (2)). By contrast, the reaction carried out in dichloromethane led to [Ti{μ-N,O-NTs}Cl(NMe2)(NHMe2)2]2 (3) and [Ti{μ-N,O-NTs}Cl2(NHMe2)2]n (4) through solvent activation. The same reaction of M(NMe2)4/TsNH2 conducted in the presence of an excess of trimethylchlorosilane produced [V(NTs)Cl2(NHMe2)2] (5) and [(Me2HN)Cl2Ti(μ2-N-NTs-κ2N,O)2TiCl2(NHMe2)2] (6). Alternatively, compound 6 has also been prepared from TiCl2(NMe2)2 and TsNH2. 1 was reacted with trimethylchlorosilane to afford the amide complex [Ti{μ-N,O‘-N(SiMe3)Ts-κ3N,O,O‘}Cl2(NMe2)]2 (7) in which the tosylimide bond has been silylated. Compounds 1−6 represents the first examples of sulfonylimido complexes for titanium and vanadium.