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Mechanistic dichotomies in redox reactions of mononuclear metal-oxygen intermediates

Authors
Fukuzumi, ShunichiCho, Kyung-BinLee, Yong-MinHong, SeungwooNam, Wonwoo
Issue Date
Dec-2020
Publisher
ROYAL SOC CHEMISTRY
Citation
CHEMICAL SOCIETY REVIEWS, v.49, no.24, pp 8988 - 9027
Pages
40
Journal Title
CHEMICAL SOCIETY REVIEWS
Volume
49
Number
24
Start Page
8988
End Page
9027
URI
https://scholarworks.sookmyung.ac.kr/handle/2020.sw.sookmyung/1008
DOI
10.1039/d0cs01251c
ISSN
0306-0012
1460-4744
Abstract
There are mechanistic dichotomies with regard to the formation, electronic structures and reaction mechanisms of metal-oxygen intermediates, since these metal-oxygen species could be composed of different resonance structures or canonical structures of the oxidation states of metals and ligands, which may undergo different reaction pathways. Even the same metal-oxygen intermediates, such as metal-oxo species, may undergo an electron-transfer pathway or a direct hydrogen or oxygen atom transfer pathway depending on the one-electron redox potentials of metal-oxo species and substrates. Electron-transfer pathways are also classified into two mechanisms, such as outer-sphere and inner-sphere pathways. The one-electron redox potentials of metal-oxygen species and substrates are also shifted because of the binding of acids, which can result from either hydrogen bonding or protonation. There are a rebound pathway and a non-rebound pathway following the initial electron transfer or hydrogen atom transfer step to produce hydroxylated products, depending on the one-electron redox potentials of metal-oxo species and substrates. Nucleophilic reactions can be switched to electrophilic pathways, depending on reaction conditions such as reaction temperature. Spin states of metal-oxygen intermediates are also an important factor that controls the redox reactivity of oxidants in oxidation reactions. Here, we review such various mechanistic dichotomies in redox reactions of metal-oxygen intermediates with the emphasis on understanding and controlling the redox reactivity of metal-oxygen intermediates from experimental and theoretical points of view.
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