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High-valent metal-oxo complexes generated in catalytic oxidation reactions using water as an oxygen source

Title
High-valent metal-oxo complexes generated in catalytic oxidation reactions using water as an oxygen source
Authors
Fukuzumi S.Kojima T.Lee Y.-M.Nam W.
Ewha Authors
남원우Shunichi Fukuzumi이용민
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus
Issue Date
2017
Journal Title
Coordination Chemistry Reviews
ISSN
0010-8545JCR Link
Citation
vol. 333, pp. 44 - 56
Keywords
Electron transferHigh-valent metal-oxo complexesPhotocatalystPhotoinduced electron transferRedox catalysis
Publisher
Elsevier B.V.
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
High-valent metal-oxo complexes are produced by successive electron-transfer oxidation of metal complexes with one-electron oxidants in the presence of water, which is an oxygen source in the generation of the metal-oxo complexes. Then, metal-oxo complexes oxidize substrates to yield oxygenated substrates, accompanied by the regeneration of reduced metal complexes. Thus, the oxidation of substrates using one-electron oxidants can be catalyzed by metal complexes via formation of high-valent metal-oxo complexes by the electron-transfer oxidation of metal complexes in the presence of water as an oxygen source. When water is used as a substrate, water is oxidized by one-electron oxidants to evolve dioxygen via an O[sbnd]O bond formation process. The one-electron oxidants used for the formation of high-valent metal-oxo complexes can be replaced by much weaker oxidants, when a photosensitizing metal complex, such as [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine), is employed as a photocatalyst, an oxidized form of the photocatalyst, which is generated via photoinduced electron transfer from the excited state to a weaker oxidant, can oxidize metal complexes in the presence of water to afford the high-valent metal-oxo complexes. Thus, the oxidation of substrates, including water oxidation, by weak oxidants can be catalyzed by metal complexes under photoirradiation of the photocatalyst using water as an oxygen source. © 2016 Elsevier B.V.
DOI
10.1016/j.ccr.2016.09.018
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자연과학대학 > 화학·나노과학전공 > Journal papers
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