High-valent Metal-oxo Intermediates in Energy Demanding Processes: from Dioxygen Reduction to Water Splitting

Four-electron reduction of dioxygen to water and splitting of water to dioxygen are extremely important processes in the context of attaining clean renewable energy sources. High-valent metal-oxo cores are proposed as reactive intermediates in these vital processes, although they have only been isolated in extremely rare cases in the biological systems thereby making the mechanism ambiguous. Recent biomimetic studies have, however, aided in our understanding of the fundamental reactivity of the high-valent metal-oxo species in various reactions relevant to energy conversion. All these studies are summarized in the present review.