Synthetic analogues and computationally assisted structure-function analyses have been used to explore the features that control proton-electron and proton-hydride coupling in electrocatalysts inspired by the [NiFe]-hydrogenase active site. Of the bimetallic complexes derived from aggregation of the dithiolato complexes MN2S2 (N2S2 = bismercaptoethane diazacycloheptane; M = Ni or Fe(NO)) with (eta(5)-C5H5)Fe(CO)(+) (the Fe ' component) or (eta(5)-C5H5)Fe(CO)(2)(+), Fe '', which yielded Ni-Fe'+, Fe-Fe'+, Ni-Fe ''+, and Fe-Fe ''+, respectively, both Ni-Fe '+ and Fe-Fe '+ were determined to be active electrocatalysts for H-2 production in the presence of trifluoroacetic acid. Correlations of electrochemical potentials and H-2 generation are consistent with calculated parameters in a predicted mechanism that delineates the order of addition of electrons and protons, the role of the redox-active, noninnocent NO ligand in electron uptake, the necessity for Fe'-S bond breaking (or the hemilability of the metallodithiolate ligand), and hydride-proton coupling routes. Although the redox active {Fe(NO)}(7) moiety can accept and store an electron and subsequently a proton (forming the relatively unstable Fe-bound HNO), it cannot form a hydride as the NO shields the Fe from protonation. Successful coupling occurs from a hydride on Fe' with a proton on thiolate S and requires a propitious orientation of the H-S bond that places H+ and H- within coupling distance. This orientation and coupling barrier are redox-level dependent. While the Ni-Fe' derivative has vacant sites on both metals for hydride formation, the uptake of the required electron is more energy intensive than that in Fe-Fe' featuring the noninnocent NO ligand. The Fe'-S bond cleavage facilitated by the hemilability of thiolate to produce a terminal thiolate as a proton shuttle is a key feature in both mechanisms. The analogous Fe ''-S bond cleavage on Ni-Fe '' leads to degradation.