Vanadium nitride functionalization and denitrogenation by carbon disulfide and dioxide

A dramatic difference in behavior is observed for the dithiocarbamate and carbamate complexes [Ar(Bu-t)N](3)V(NCE2)Na(THF)(2) (E = S or O, respectively), prepared from the corresponding nitride species {[Ar(Bu-t)N](3) V equivalent to NNa}(2) by way of a nucleophilic addition reaction involving carbon disulfide or dioxide, and is rationalized with the aid of DFT calculations.