Mechanistic dichotomies in redox reactions of mononuclear metal-oxygen intermediates
- 등재 SCIE, SCOPUS
- 발행기관 Royal Society of Chemistry
- 발행년도 2020
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000175323
- 본문언어 영어
- Published As http://dx.doi.org/10.1039/d0cs01251c
- PubMed https://pubmed.ncbi.nlm.nih.gov/33316016
초록/요약
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. This journal is © The Royal Society of Chemistry.
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