An N-heterocyclic carbene containing [FeFe]H(2)ase model complex, whose X-ray structure displays an apical carbene, shows an unexpected two-electron reduction to be involved in its electro-catalytic dihydrogen production. Density functional calculations show, in addition to a one-electron Fe-Fe reduction, that the aryl-substituted N-heterocyclic carbene can accept a second electron more readily than the Fe-Fe manifold. The juxtaposition of these two one-electron reductions resembles the [FeFe]H(2)ase active site with an FeFe di-iron unit joined to the electroactive 4Fe4S cluster.