Compounds [Fe₂{𝜇-pydt}(CO)₆] (pydt = pyrazine-2,3-dithiolate) (1), [Fe₂{𝜇-qdt}(CO)₆] (qdt = quinoxaline-2,3-dithiolate) (2), [Fe₂{𝜇-ppdt}CO)₆] (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) (3), [Fe₂{𝜇-pydt}(CO)₅PPh₃] (4), [Fe₂{𝜇-qdt}(CO)₅PPh₃] (5) and [Fe₂{𝜇-ppdt}(CO)₅PPh₃] (6) have been synthesized in order to model the active sites of `[FeFe]-hydrogenase’. Compounds 1–6 have been characterized by routine spectral studies and unambiguously by single crystal X-ray crystallography. Supramolecular chemistry of compounds 1–6 have been described in terms of intermolecular interactions, observed in their respective crystal structures. Electro-catalytic hydrogen evaluation studies (from acetic acid) have been performed using compounds 1–6 as electro-catalysts. The mechanistic aspects of relevant electro–catalytic proton reductions have been discussed in detail.