Dioxygen activation by mononuclear nonheme iron(II) complexes generates iron-oxygen intermediates in the presence of an NADH analogue and proton

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Hong, Seungwoo [1 ,2 ]
Lee, Yong-Min [1 ]
Shin, Woonsup [2 ]
Fukuzumi, Shunichi [3 ]
Nam, Wonwoo [1 ]
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[1] Department of Chemistry and Nano Science, Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea, Republic of
[2] Department of Chemistry, Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742, Korea, Republic of
[3] Department of Material and Life Science, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan
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(Chemical Equation Presented) One primary goal in biomimetic research is to understand mechanisms of dioxygen activation; structures of reactive intermediates; and reactivities of the intermediates involved in catalytic oxidation reactions by metalloenzymes; such as heme and nonheme iron oxygenases. In this communication; we have reported the first example of generating nonheme iron(III)-hydroperoxo and iron(IV)-oxo complexes by activating O2 with a biologically important electron donor; an NADH analogue; and an acid. The formation of iron(III)-hydroperoxo and iron(IV)-oxo complexes was found to depend on the supporting ligands. We have also demonstrated that high-spin nonheme iron(II) complexes with a low oxidation potential are able to bind and activate O2 to generate the iron-oxygen intermediates. © 2009 American Chemical Society;
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页码:13910 / 13911
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