Reduction of the two trivalent 2,6-{[2,6-(i-Pr)(2)C6H5]N=C(CH3)](2)(C5H3N)VCl3 and [2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]-VCI(THF) complexes with excess NaH afforded two corresponding end-on dinitrogen-bridged complexes [2,6-{[2,6-(i-Pr)(2)C6H5]N=C(CH3)}(2)(C5H3N)V](2)(m-N-2).(hexane) (1) and [{[2,6-{[2,6-(i-Pr)(2)C6H3)N-C=(CH2)}(2)(C5H3N)]V](2)(m-N-2).(hexane) (3). Despite their very close structural similarity, the two species have completely different natures. The first is paramagnetic and may be regarded as generated by the two-electron attack of two formally zerovalent vanadium moieties on the same N-2 unit. In the nearly diamagnetic 3 instead, the N2 unit has been reduced by two vanadium atoms, formally divalent. Structural analysis and DFT calculations have indicated that partial reduction of the bridging nitrogen occurred for both complexes while, in the case of 1, substantial metal-to-ligand electron transfer also occurs.