We present in this work a convergent synthetic approach to vanadium complexes bearing a terminal nitride ligand, namely complexes of the type (nacnac)V(N)(X) (nacnac- = [ArNC(Me)]2CH, Ar = 2,6-iPr2C6H3, X- = amide, or alkoxide ligand).  We also provide compelling evidence for how these nitrides are formed, in part provided by a series of crossover and synthetic experiments.  Incorporation of the nitride ligand involves an unprecedented bimolecular pathway whereby nitrogen loss is promoted by a Lewis acid.  In addition, reactivity studies surrounding the terminal nitride ligand are reported.  Although the nitride motif has nucleophilic character, this one atom ligand can serve as a bridge for electron transfer, thus promoting the reduction of the vanadium(5+) metal ion with concurrent oxidation of the incoming substrate.

Understanding the formation of vanadium complexes having a terminal nitride ligand: A one-atom ligand conduit for electron transfer

243rd National Meeting (2012)

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