Phenylthiolate-Diironhexacarbonyl Complexes: A Comparative Conceptual DFT and Electrochemical Study
The electrocatalytic reduction of acetic acid by the previously studied [(Î¼-biphenyl-2,2€²-dithiolato)2Fe2(CO)6 (1), has been explored. Complex 1 generates hydrogen at -2.53 V versus Fc/Fc+. Comparatively, the overpotential for the reduction of protons to hydrogen by 1 (1.07 V vs Fc/Fc+) is higher by 270 mV than that of the non-bridging analog [(Î¼-SPh)2Fe2(CO)6 (2). Global reactivity descriptors, chemical hardness and electrophilicity index for 1 and 2 have been computed from frontier molecular orbital energies determined using HF and DFT/B3LYP methods. The results indicate that complex 1 is softer with a higher electrophilicity index than 2, in agreement with the minimum electrophilicity principle.
Transition Metal Chemistry
Wisener, Jazlynn C.; Patton, Kaitlin T.; Agbo, Johnson K.; and Mebi, Charles A., "Phenylthiolate-Diironhexacarbonyl Complexes: A Comparative Conceptual DFT and Electrochemical Study" (2016). Faculty Publications - Physical Sciences. 29.