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

107 Scopus citations

Abstract

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. This journal is

Original languageEnglish
Pages (from-to)4804-4811
Number of pages8
JournalChemical Society Reviews
Volume50
Issue number8
DOIs
StatePublished - 21 Apr 2021

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842) to W. N. and Basic Science Research Program (NRF-2020R1I1A1A01074630) to Y.-M. L., the Deutsche Forschungsgemein-schaft (DFG, German Research Foundation) under Germany’s Excellence Strategy – EXC 2008 – 390540038 – (UniSysCat) and the Heisenberg-Professorship to K. R., Xi’an Key Laboratory of Organometallic Material Chemistry to W. N., Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University (by the Ministry of Education of China), National Natural Science Foundation of China (21573139 and 21773146), Fundamental Research Funds for the Central Universities, and the Research Funds of Shaanxi Normal University

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842) to W. N. and Basic Science Research Program (NRF-2020R1I1A1A01074630) to Y.-M. L., the Deutsche Forschungsgemein-schaft (DFG, German Research Foundation) under Germany's Excellence Strategy – EXC 2008 – 390540038 – (UniSysCat) and the Heisenberg-Professorship to K. R., Xi'an Key Laboratory of Organometallic Material Chemistry to W. N., Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University (by the Ministry of Education of China), National Natural Science Foundation of China (21573139 and 21773146), Fundamental Research Funds for the Central Universities, and the Research Funds of Shaanxi Normal University of China to R. C., and National Natural Science Foundation of China (22003036) to X.-P. Z.

Funding Information:
of China to R. C., and National Natural Science Foundation of China (22003036) to X.-P. Z.

Publisher Copyright:
© The Royal Society of Chemistry.

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