Proposed catalytic pathway for H2 evolution mediated by LN2S2NiIIFeII at the catalytic wave. After a one-electron reduction, LN2S2NiIIFeII generates LN2S2NiIFeII, a mimic of the Ni-L state, which is then further reduced to afford the metal-radical complex LN2S2•NiIFeII. The latter reacts with protons to yield the metal-hydride complex LN2S2NiII(H)FeII, a model of Ni-R, which is protonated to produce H2 with concomitant regeneration of the initial LN2S2NiIIFeII complex.