The potential energy surfaces corresponding to the dehydration reaction of NH3 by VO+ ((3)Sigma, (1)Delta, (5)Sigma) and FeO+ ((6)Sigma, (4)Delta) metal oxide cations have been investigated within the framework of the density functional theory in its B3LYP formulation and by employing new optimized basis sets for iron and vanadium. The reaction is proposed to occur through two hydrogen shifts from the nitrogen to the oxygen atom giving rise to multicentered transition states. Possible spin crossing between surfaces at different spin multiplicities has been considered. The energy profiles are compared with the corresponding ones for the insertion of bare cations to investigate the influence on reactivity of the presence of the oxygen ligand, The topological analysis of the gradient field of the electron localization function has been used to characterize the nature of the bonds for all the minima and transition states along the paths.