Unveiling the High Catalytic Activity of a Dinuclear Iron Complex for the Oxygen Evolution Reaction

The dinuclear iron complex [(H₂O)-Fe^III-(ppq)-O-(ppq)-Fe^III-Cl]³⁺ (Fe^III(ppq), ppq = 2-(pyrid-2'-yl)-8-(1″,10″-phenanthrolin-2″-yl)-quinoline) demonstrates a catalytic activity about one order of magnitude higher than the mononuclear iron complex [Cl-Fe^III(dpa)-Cl]⁺ (Fe^III(dpa), dpa = N,N-di(1,10-phenanthrolin-2-yl)-N-isopentylamine) for the oxygen evolution reaction (OER). However, the mechanism behind such an unusually high activity has remained largely unclear. To solve this puzzle, a decomposition-and-reaction mechanism is proposed for the OER with the dinuclear Fe^III(ppq) complex as the initial state of the catalytic agent. In this mechanism, the high-valent dinuclear iron complex first dissociates into two mononuclear moieties, and the oxidized mononuclear iron complexes directly catalyze the formation of an O-O bond through a nitrate attack pathway with nitrate functioning as a cocatalyst. Density functional theory calculations reveal that it is the electron-deficient microenvironment around the iron center that gives rise to the remarkable catalytic activity observed experimentally. Therefore, the outstanding performance of the Fe^III(ppq) catalyst can be ascribed to the high reactivity of its mononuclear moieties in a high oxidation state, which is concomitant with the structural stability of the low-valent dinuclear complex. The theoretical insights provided by this study could be useful for the optimization and design of novel iron-based water oxidation catalysts.