Oxidation of hydroquinones by a nonheme iron(IV)-oxo species

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• 作者：Kasi Nehru ; Yukyeong Jang ; Sunok Oh ; Fré ; dé ; ric Dallemer ; Wonwoo Nam ; Jinheung Kim
• 关键词：Nonheme iron enzymes ; High-valent iron-oxo species ; Oxidation ; Hydroquinone ; Hydrogen-atom abstraction
• 刊名：Inorganica Chimica Acta
• 出版年：2008
• 出版时间：2 June 2008
• 年：2008
• 卷：361
• 期：8
• 页码：2557-2561
• 全文大小：190 K

文摘

The reactivity of an isolated, well-characterized nonheme iron(IV)-oxo complex, [(TMC)Fe^IVO]²⁺ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), has been examined in the oxidation of hydroquinones. This complex has been shown to oxidize a series of hydroquinones, resulting in the production of the corresponding quinone products. Kinetic studies performed with substituted hydroquinones revealed a good correlation between reaction rates of the iron(IV)-oxo complex and the electron-donating ability of the substituents and the bond dissociation energy (BDE) of substrate O–H bonds. These results with a kinetic isotope effect (KIE) of 2.7 led us to propose a hydrogen-atom abstraction mechanism for the oxidation of hydroquinones by the nonheme iron(IV)-oxo species.