| Abstract: | Lithium bis(trimethylsilyl)amide, LiN(SiMe3)2, reacts with Cp*V(O)Cl2 and Cp*TaCl4 to give trimethylsilylimido complexes such as Cp*V(NSiMe3)(μ‐NSiMe3)]2 ( 7 ) and Cp*Ta(Cl)(NSiMe3)N(SiMe3)2] ( 19 ), respectively. Substitution of the chloro ligand in 19 by anionic groups leads to complexes with 3 different N‐containing ligands, Cp*Ta(X)(NSiMe3)N(SiMe3)2] (X = N3 ( 20 ) or NPEt3 ( 21 )). Complex 7 is air‐ and moisture‐sensitive, and several derivatives containing oxo and trimethylsiloxy ligands have been identified. Trimethylsilyl azide, Me3Si‐N3, is able to replace the oxygen‐containing ligands for azido ligands. The two complete series of bis(azido)‐bridged complexes, Cp*VCln(N3)2‐n(μ‐N3)]2 (n = 2, 1, 0) and Cp*TaCln(N3)3‐n(μ‐N3)]2(n = 3, 2, 1, 0), are accessible from the reactions of Cp*VCl3 and Cp*TaCl4, respectively, with trimethylsilyl azide. A bis(nitrido)‐bridged azido‐vanadium complex, Cp*V(N3)(μ‐N)]2 ( 18 ), has also been obtained and structurally characterized. |
