Journal
CHEMICAL SOCIETY REVIEWS
Volume 49, Issue 24, Pages 8988-9027Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0cs01251c
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Funding
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- Basic Science Research Program [NRF-2020R1I1A1A01074630]
- MSIP [NRF-2020R1C1C1008886]
- JSPS KAKENHI from MEXT, Japan [16H02268]
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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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