Development of functionality of metal complexes based on proton-coupled electron transfer
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- Kojima Takahiko
- Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba
Bibliographic Information
- Other Title
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- プロトン共役電子移動に基づく金属錯体の機能創出
- Award Accounts プロトン共役電子移動に基づく金属錯体の機能創出
- Award Accounts プロトン キョウヤク デンシ イドウ ニ モトズク キンゾク サクタイ ノ キノウ ソウシュツ
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Abstract
<p>Proton-coupled electron transfer (PCET), in which a proton and an electron are directed to respective accepting sites separately, is a fundamental process as observed in many kinds of redox reactions including biological and chemical processes. PCET oxidation of Ru(II)-aqua complexes has been applied for the formation of Ru(IV)-oxo, Ru(III)-hydroxo, and novel Ru(III)-oxyl complexes as reactive species in oxidation reactions of organic substrates and mechanistic insights into the reactions are gained on the basis of kinetic analysis. Ru(III)-pterin complexes without oxo ligands can accept hydrogen from O–H and C–H bonds of substrates and the reactivity and transition states of hydrogen-atom transfer reactions are revealed to be controlled by the proton acceptability and electron acceptability of the hydrogen acceptors; this is also valid for Ru(IV)-oxo complexes. Intramolecular PCET also enables to establish novel molecular bistability to regulate the direction of electron transfer and to create unprecedented electronic structures of metal complexes.</p>
Journal
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- Bulletin of Japan Society of Coordination Chemistry
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Bulletin of Japan Society of Coordination Chemistry 74 (0), 9-18, 2019-11-30
Japan Society of Coordination Chemistry