Synthesis and Characterization of Group 4 Amide Chloride and Amide Imide Complexes

Group 4 amide chloride complexes (Me2N)2Hf[N(SiMe3)2]Cl (1b), [(Me3Si)2N]2MCl2Li(THF)3Cl (M = Zr, 2a; Hf, 2b), and [(Me3Si)2N]2MCl2(THF) (M = Zr, 3a; Hf, 3b) and their X-ray crystal structures are reported. An improved synthesis of {[(Me3Si)2N]Ti(μ-NSiMe3)Cl}2 (4) and its use to prepare amide imide {[(Me3Si)2N]Ti(μ-NSiMe3)(NMe2)}2 (5) are also presented. X-ray crystal structures of 5 and previously reported complexes (Me2N)2Zr[N(SiMe3)2]Cl (1a), [(Me3Si)2N]2TiCl2 (6), and [(Me3Si)2N]ZrCl3(THF)2 (7) have been determined. Both 1a and 1b are dimers {[(Me3Si)2N]-(Me2N)2M(μ-Cl)}2 (M = Zr, Hf) in the solid state.