Tracking an FeV(O) Intermediate for Water Oxidation in Water

Abstract

AbstractHigh‐valent iron‐oxo species are appealing for conducting O−O bond formation for water oxidation reactions. However, their high reactivity poses a great challenge to the dissection of their chemical transformations. Herein, we introduce an electron‐rich and oxidation‐resistant ligand, 2‐[(2,2′‐bipyridin)‐6‐yl]propan‐2‐ol to stabilize such fleeting intermediates. Advanced spectroscopies and electrochemical studies demonstrate a high‐valent FeV(O) species formation in water. Combining kinetic and oxygen isotope labelling experiments and organic reactions indicates that the FeV(O) species is responsible for O−O bond formation via water nucleophilic attack under the real catalytic water oxidation conditions.