Preparation, Characterization, and Reactivity of a Diamagnetic Vanadium Nitride

The reactions of (Ph 2 N) 3 V‐(THF) ( 1 ) with [(CH 3 ) 3 Si]N 3 and [(CH 3 ) 3 Si]CHN 2 proceed at room temperature to afford the corresponding derivatives (Ph 2 N) 3 V[N‐Si(CH 3 ) 3 ] ( 2a ) and (Ph 2 N) 3 V[N 2 CHSi(CH 3 ) 3 ] ( 3 ). Reactions of both 2a and 3 with lithium isopropylamide provide the unprecedented anionic vanadium nitride species [(Ph 2 N) 3 V(μ‐N)Li(THF) 3 ]·(THF) 0.5 ( 4 ), which displays moderate nucleophilicity. It reacts with (CH 3 ) 3 SiCl and Mel to reform the complex (Ph 2 N) 3 V(N‐R) [R = Si(CH 3 ) 3 ( 2a ), Me ( 2b )]. Reactions with Cp 2 ZrCl 2 and CpTiCl 3 lead to the formation of the heterodinuclear bridged nitride complexes [(Ph 2 N) 3 V(μ‐N)ZrClCp] 2 ] [Cp = Cp]=Cp ( 6a ), CH 3 C 5 H 4 ( 6b )] and [{(Ph 2 N) 3 V(μ‐N)} 2 TiClCp] ( 8 ).