The potential energy surfaces for the reaction of first-row transition metal cations Ti(+)((4)F,(2)F), V(+)((5)D,(3)F), and Cr(+)((6)S,(4)D) with NH(3) and CH(4) have been built up by using density functional theory. In all cases, the high-spin ion-dipole complex, which is the most stable species on the respective potential energy hypersurfaces, is initially formed. In the second step, a hydrogen shift process leads to the formation of the insertion products, which are more stable in a low-spin state. From these intermediates three dissociation channels have been considered. All the results have been compared with existing experimental and theoretical data and our earlier work on the reactivity of Sc(+), to clarify similarities and differences in the behavior of the transition metal ions considered.