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]−.