Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750 (Korea).
Angew Chem Int Ed Engl. 2014 Jul 21;53(30):7843-7. doi: 10.1002/anie.201404556. Epub 2014 Jun 10.
One-electron reduction of mononuclear nonheme iron(III) hydroperoxo (Fe(III)-OOH) and iron(III) alkylperoxo (Fe(III)-OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one-electron reduced iron(II) (hydro/alkyl)peroxo species is the rate-determining step, followed by the heterolytic O-O bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic O-O bond-cleavage mechanism. The present results provide the first example showing the one-electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic O-O bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions.
亚铁衍生物对单核非血红素铁（III）过氧氢（Fe（III）-OOH）和铁（III）烷过氧（Fe（III）-OOR）配合物的单电子还原导致相应的铁（IV）氧代配合物的形成。转化速率取决于电子供体的浓度和氧化电位，因此表明铁（III）（氢/烷基）过氧配合物向其单电子还原的铁（II）（氢/烷基）过氧物种的还原是速率决定步骤，随后是假定的铁（II）（氢/烷基）过氧物种的异裂 O-O 键断裂，生成铁（IV）氧代配合物。产物分析支持异裂 O-O 键断裂机制。目前的结果提供了第一个例子，表明铁（III）（氢/烷基）过氧配合物的单电子还原和铁（II）（氢/烷基）过氧物种的异裂 O-O 键断裂形成铁（IV）氧代中间体，这些中间体发生在非血红素铁酶和芬顿反应中。
