The addition of mild electrophiles to the anionic terminal Mo-nitride {[(BuOCO)-Bu-t]Mo N]Na(DMF)}(2) (1) and the synthesis of nitriles via metal-mediated N-atom transfer is reported. The X-ray structure of a pivaloylimido intermediate indicates the presence of a weakly coordinated DMF molecule. Kinetic studies confirm that cyclometalation and DMF dissociation Occur prior to nitrile extrusion.