Synthesis of Mono‐Imido Tungsten Complexes Directly from WCl 6

A new series of tungsten complexes were prepared using WCl 6 , N ‐ tert ‐butyltrimethylsilylamine, and amide ligands as potential precursors for WN x thin film deposition. The complexes [W(N t Bu)(NMe 2 ) 4 ] ( 2 ), [W(N t Bu)(MeNCH 2 CH 2 NMe) 2 ] ( 3 ), [W(N t Bu)(MeNCH 2 CH 2 CH 2 NMe) 2 ] ( 4 ), [W(N t Bu)( i PrNCH 2 CH 2 N i Pr) 2 ] ( 5 ), and [W(N t Bu)( t BuNCH 2 CH 2 N t Bu) 2 ] ( 6 ) were prepared by a two‐step process. First, the controlled reaction between WCl 6 and N ‐ tert ‐butyltrimethylsilylamine afforded the complex [W(N t Bu)Cl 4 (py)] ( 1 ) from which the substitution of chloride ions with the corresponding amide ligands gave complexes 2 – 6 . Single crystal X‐ray crystallography showed that complex 1 crystalized in the triclinic space group P ‐1 with an octahedral structure. Among complexes 2 – 6 , complexes 4 and 5 exhibited good volatility and stability.