Carboxamide Fe(III) complex as the electrocatalyst of water oxidation reaction: WNA and I2M O-O bond formation pathways

A single-site Fe(III) carboxamide complex, [Fe(HbpH) (Cl)2] (1), (HbpH = N,N '-Bis(picolinoyl)hydrazine) anion), was synthesized and used as the electrocatalyst of water oxidation reaction. Complex 1 catalyzes the oxidation of water to O2 at the pH of 8 in phosphate buffer solution with the onset of a catalytic wave at about 0.45 V versus RHE with the turnover frequency (TOF) of 5.8 s-1 at room temperature. The stability of the catalyst in water oxidation processes by electrochemical and UV-vis measurements, demonstrated the realistic molecular electrocatalysis of 1. Differential pulse voltammetry (DPV) of 1 in different pH values showed the dependency of oxidation potential to the pH of the environment, establishing the fact that the catalytic cycle involves the proton-coupled electron transfer (PCET) process. Density functional theory (DFT) calculations on the mechanism of water oxidation process of 1 shows that the oxygen evolution reaction is carried out through the water nucleophilic attack (WNA) to the metal center ion, resulted to the formation of FeIV(O) species. Also, DFT cal-culations showed that the formation of an O-O bond proceeds through the interaction two molecular mechanism (I2M), which compete with the WNA mechanism following from experimental analysis. The electroactivity of the metal centre and carboxamide ligand and the ability of the ligand to stabilize the high oxidation numbers of the metal-ion centre during the oxidation process, provide different oxidation pathways for an OER process.