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Dioxygen activation chemistry by synthetic mononuclear nonheme iron, copper and chromium complexes

Title
Dioxygen activation chemistry by synthetic mononuclear nonheme iron, copper and chromium complexes
Authors
Hong, SeungwooLee, Yong-MinRay, KallolNam, Wonwoo
Ewha Authors
남원우이용민
SCOPUS Author ID
남원우scopus; 이용민scopusscopus
Issue Date
2017
Journal Title
COORDINATION CHEMISTRY REVIEWS
ISSN
0010-8545JCR Link1873-3840JCR Link
Citation
vol. 334, pp. 25 - 42
Keywords
MetalloenzymesBiomimeticsDioxygen activationMetal-oxygen intermediateNonheme models
Publisher
ELSEVIER SCIENCE SA
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The activation of dioxygen (O-2) by metalloenzymes proceeds by binding O-2 at their active sites and then generating highly reactive, thermally unstable metal-oxygen intermediates, such as metal-superoxo, -(hydro)peroxo and-oxo species, via electron and proton transfer reactions. The synthesis, characterization and reactivity studies of the chemical model compounds of the key metal-oxygen intermediates can provide vital insights into the chemistry of such enzymatic reactions, and our understanding of the biologically important metal-oxygen intermediates has improved greatly by the success of synthesizing their analogues recently. In this article, we provide a focused review on the recent advances in the dioxygen activation processes at biomimetic iron, copper and chromium centers, paying particular emphasis to the factors that control the O-2-activation reactions, such as the effects of ligands, redox potentials and spin-states of biomimetic compounds. Among the most significant findings of these studies are the use of O-2 as an oxygen source in the generation of iron-oxygen intermediates and the autocatalytic radical chain reactions involved in the iron-mediated O-2-activation processes. Similarly, new approaches to achieve less overpotential have been identified, which is more desirable for the catalytic four-electron reduction of O-2 using copper complexes. In addition, the versatility of metal-superoxo species as reactive intermediates in various oxidation reactions has been elegantly demonstrated in the recent synthesis of a mononuclear nonheme chromium(III)-superoxo complex. This review will provide clues that lesson us how synthetic and mechanistic developments in biomimetic research can advance our understanding of O-2-activation processes in enzymatic reactions. (C) 2016 Elsevier B.V. All rights reserved.
DOI
10.1016/j.ccr.2016.07.006
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자연과학대학 > 화학·나노과학전공 > Journal papers
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