Electrochemical Formation of Fe^V(O) and Mechanism of Its Reaction with Water During O−O Bond Formation

Abstract

A detailed electrochemical investigation of a series of iron complexes (biuret-modified tetraamido iron macrocycles Fe^III -bTAML), including the first electrochemical generation of Fe^V (O), and demonstration of their efficacy as homogeneous catalysts for electrochemical water oxidation (WO) in aqueous medium are reported. Spectroelectrochemical and mass spectral studies indicated Fe^V (O) as the active oxidant, formed due to two redox transitions, which were assigned as Fe^IV (O)/Fe^III (OH₂ ) and Fe^V (O)/Fe^IV (O). The spectral properties of both of these high-valent iron oxo species perfectly match those of their chemically synthesised versions, which were thoroughly characterised by several spectroscopic techniques. The O-O bond-formation step occurs by nucleophilic attack of H₂ O on Fe^V (O). A kinetic isotope effect of 3.2 indicates an atom-proton transfer (APT) mechanism. The reaction of chemically synthesised Fe^V (O) in CH₃ CN and water was directly probed by electrochemistry and was found to be first-order in water. The pK_a value of the buffer base plays a critical role in the rate-determining step by increasing the reaction rate several-fold. The electronic effect on redox potential, WO rates, and onset overpotential was studied by employing a series of iron complexes. The catalytic activity was enhanced by the presence of electron-withdrawing groups on the bTAML framework. Changing the substituents from OMe to NO₂ resulted in an eightfold increase in reaction rate, while the overpotential increased threefold.