Nitrogen Atom Transfer from a Dinitrogen-Derived Vanadium Nitride Complex to Carbon Monoxide and Isocyanide

Reduction
of [(ONO)­V­(THF)] with KH under an N2 atmosphere
cleaves the NN bond to afford a bis­(μ-nitride) V­(IV)
dimer. This complex is oxidized to generate a V­(V) nitride. The reactions
of the V­(V) nitride with carbon monoxide and isocyanide led to formation
of cyanate and carbodiimide complexes. Following treatment of the
cyanate complex with alkyne produces an alkyne adduct along with the
release of potassium cyanate. Dissolution of the alkyne adduct in
THF regenerates the starting complex [(ONO)­V­(THF)], thereby closing
a synthetic cycle for conversion of N2 and CO into [NCO]−.