Tracking an Fe-V(O) Intermediate for Water Oxidation in Water

High-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 & PRIME;-bipyridin)-6-yl]propan-2-ol to stabilize such fleeting intermediates. Advanced spectroscopies and electrochemical studies demonstrate a high-valent Fe-V(O) species formation in water. Combining kinetic and oxygen isotope labelling experiments and organic reactions indicates that the Fe-V(O) species is responsible for O-O bond formation via water nucleophilic attack under the real catalytic water oxidation conditions.

Automated summary

In this work, an electron-rich and oxidation-resistant ligand was introduced to stabilize high-valent iron-oxo species for water oxidation reactions. Advanced spectroscopies and electrochemical studies revealed the formation of a high-valent Fe-V(O) species in water. Kinetic and oxygen isotope labelling experiments, along with organic reactions, demonstrated that the Fe-V(O) species is responsible for O-O bond formation via water nucleophilic attack under real catalytic water oxidation conditions.