Participation of multioxidants in the pH dependence of the reactivity of ferrate(VI)

Takashi Kamachi, Tomohisa Kouno, Kazunari Yoshizawa

研究成果: Contribution to journalArticle査読

53 被引用数 (Scopus)


Alcohol oxidation by ferrate (FeO42-) in water is investigated from B3LYP density functional theory calculations in the framework of polarizable continuum model. The oxidizing power of three species, nonprotonated, monoprotonated, and diprotonated ferrates, was evaluated. The LUMO energy levels of nonprotonated and monoprotonated ferrates are greatly reduced by solvent effects, and as a result the oxidizing power of these two species is increased enough to effectively mediate a hydrogen-atom abstraction from the C-H and O-H bonds of methanol. The oxidizing power of these oxidants increases in the order nonprotonated ferrate < monoprotonated ferrate < diprotonated ferrate. The reaction pathway is initiated by C-H bond activation, followed by the formation of a hydroxymethyl radical intermediate or an organometallic intermediate with an Fe-C bond. Kinetic aspects of this reaction are analyzed from calculated energy profiles and experimentally known pK a values. The pH dependence of this reaction in water is explained well in terms of a multioxidant scheme.

ジャーナルJournal of Organic Chemistry
出版ステータス出版済み - 5 27 2005

All Science Journal Classification (ASJC) codes

  • 有機化学


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