Transition metal-mediated O-O bond formation and activation in chemistry and biology

Xue Peng Zhang, Anirban Chandra, Yong Min Lee, Rui Cao, Kallol Ray, Wonwoo Nam

Research output: Contribution to journalReview articlepeer-review

121 Scopus citations


Oxygen evolution and reduction reactions are fundamental processes in biological energy conversion schemes, which represent an attractive method for artificial energy conversion for a world still largely depending on fossil fuels. A range of metalloenzymes achieve these challenging tasks in biology by activating water and dioxygen using cheap and abundant transition metals, such as iron, copper, and manganese. High-valent metal-oxo/oxyl, metal-superoxo, and/or metal-(hydro)peroxo species are common reactive intermediates that are found in the O-O bond formation and activation reactions. The transient nature of the metal-oxygen intermediates has, however, prevented their isolation and characterization in most cases. As a consequence, unambiguous mechanistic assignments in the O-O bond formation and cleavage processes in biological and chemical entries remain elusive, especially for the intermediates and mechanisms involved in the O-O bond formation reactions. This viewpoint article aims at summarizing the information obtained to date in enzymatic and biomimetic systems that fuels the debate regarding the nature of the active oxidants and the mechanistic uncertainties associated with the transition metal-mediated O-O bond formation and cleavage reactions.

Original languageEnglish
Pages (from-to)4804-4811
Number of pages8
JournalChemical Society Reviews
Issue number8
StatePublished - 21 Apr 2021

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© The Royal Society of Chemistry.


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