The complex �-pyrazine-2,3-dithiolato[Fe(CO)3]2 (1  ) was investigated as an electrocatalyst for H2 production from weak acids and is compared to the previously reported catalyst �-benzene-1,2-dithiolato[Fe(CO)-3]2 (2  ).  Electrochemical scan rate studies indicate that 1  ,   like 2,   shifts from a two-electron reduction at slow rates to a one-electron reduction at fast rates.  The electron withdrawing nature of the pyrazine ring causes initial reduction of 1  to occur at a more anodic potential than 2.  In addition, the overpotential for catalysis of hydrogen production from acetic acid is reduced to -0.46 V from -0.57 V.  Under a CO atmosphere 1   exhibits   two one-electron reductions and the potential for catalytic hydrogen production is shifted cathodically by 150 mV, while 2,  under the same conditions, maintains potential inversion albeit with suppressed catalytic activity.  Furthermore, DFT calculated pKa values suggest multiple protonation sites for 12-  .

Electrochemical and computational investigations of (µ-pyrazine-2,3-dithiolato)diironhexacarbonyl as a catalyst for proton reduction from weak acids

243rd National Meeting (2012)

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