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