Kinetic and thermodynamic aspects of the electrocatalysis of acid reduction in organic solvent using molecular diiron-dithiolate compounds

In an attempt to obtain molecular H-2 production electrocatalysts achieving balanced basicity and reduction potential, we focused on the mono-substituted diiron-dithiolate derivative [Fe-2(mu-bdt)(CO)(5)(P(OMe)(3))] (bdt = benzenedithiolate). The electrocatalytic efficiency of this iron-iron hydrogenase model was determined by cyclic voltammetry in acetonitrile using p-toluenesulfonic acid as a proton source. Detailed analysis of the current - potential responses and comparison with the all-CO diiron-dithiolate parent compound clearly show that the effect of the chemical properties on the electrocatalytic efficiency is not fully determined by the turnover frequency under pseudo-first-order approximation and the overpotential defined as the difference between the reduction potential of the electrocatalysts in the absence of acid and the reversible potential of the couple H-2/acid. (C) 2013 Elsevier Ltd. All rights reserved.