Facile electrocatalytic proton reduction by a [Fe-Fe]-hydrogenase bio-inspired synthetic model bearing a terminal CN ligand

An azadithiolate bridged CN − bound pentacarbonyl bis-iron complex, mimicking the active site of [Fe-Fe] H 2 ase is synthesized. The geometric and electronic structure of this complex is elucidated using a combination of EXAFS analysis, infrared and Mössbauer spectroscopy and DFT calculations. The electrochemical investigations show that complex 1 effectively reduces H + to H 2 between pH 0-3 at diffusion-controlled rates (10 11 M −1 s −1 ) i.e. 10 8 s −1 at pH 3 with an overpotential of 140 mV. Electrochemical analysis and DFT calculations suggests that a CN − ligand increases the p K a of the cluster enabling hydrogen production from its Fe( i )-Fe(0) state at pHs much higher and overpotential much lower than its precursor bis-iron hexacarbonyl model which is active in its Fe(0)-Fe(0) state. The formation of a terminal Fe-H species, evidenced by spectroelectrochemistry in organic solvent, via a rate determining proton coupled electron transfer step and protonation of the adjacent azadithiolate, lowers the kinetic barrier leading to diffusion controlled rates of H 2 evolution. The stereo-electronic factors enhance its catalytic rate by 3 order of magnitude relative to a bis-iron hexacarbonyl precursor at the same pH and potential. An azadithiolate bridged CN − bound pentacarbonyl bis-iron complex, mimicking the active site of [Fe-Fe] H 2 ase is synthesized, which effectively reduces H + to H 2 between pH 0-3 at diffusion-controlled rates (10 11 M −1 s −1 ) i.e. 10 8 s −1 at pH 3 with an overpotential of 140 mV.