单核非血红素铁模型配合物中自由基反弹的观察。
Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex.
机构信息
Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 21218 , United States.
Department of Chemistry and MacDiarmid Institute for Advanced Materials and Nanotechnology , University of Otago , P.O. Box 56, Dunedin 9054 , New Zealand.
出版信息
J Am Chem Soc. 2018 Mar 28;140(12):4191-4194. doi: 10.1021/jacs.7b12707. Epub 2018 Mar 14.
Abstract
A nonheme iron(III) terminal methoxide complex, [Fe(N3PyO)(OCH)]ClO, was synthesized. Reaction of this complex with the triphenylmethyl radical (PhC) leads to formation of PhCOCH and the one-electron-reduced iron(II) center, as seen by UV-vis, EPR, H NMR, and Mössbauer spectroscopy. These results indicate that homolytic Fe-O bond cleavage occurs together with C-O bond formation, providing a direct observation of the "radical rebound" process proposed for both biological and synthetic nonheme iron centers.
摘要
合成了一种非血红素铁（III）末端甲氧基配合物[Fe（N3PyO）（OCH）]ClO。该配合物与三苯甲基自由基（PhC）反应，生成 PhCOCH 和一电子还原的铁（II）中心，通过紫外可见光谱、电子顺磁共振光谱、核磁共振光谱和穆斯堡尔光谱可以观察到这一点。这些结果表明，Fe-O 键的均裂与 C-O 键的形成同时发生，为生物和合成非血红素铁中心提出的“自由基反弹”过程提供了直接观察。
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