Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex.

Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex.
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DOI:
10.1021/jacs.7b12707
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发表时间:
2018-03-28
影响因子:
15
通讯作者:
Goldberg DP
Goldberg DP
中科院分区:
化学1区
文献类型:
--
作者:
Pangia TM;Davies CG;Prendergast JR;Gordon JB;Siegler MA;Jameson GNL;Goldberg DP

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合成了非血红素铁(III)末端甲醇复合物[FeIII(N3PyO2Ph)(OCH3)]ClO4。该配合物与三苯甲基自由基 (Ph3C•) 的反应导致形成 Ph3COCH3 和单电子还原铁 (II) 中心,如 UV-vis、EPR、1H NMR 和穆斯堡尔光谱所示。这些结果表明,均裂 Fe-O 键断裂与 C-O 键形成同时发生,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。
A nonheme iron(III) terminal methoxide complex, [FeIII(N3PyO2Ph)(OCH3)]ClO4, was synthesized. Reaction of this complex with the triphenylmethyl radical (Ph3C•) leads to formation of Ph3COCH3 and the one-electron reduced iron(II) center, as seen by UV-vis, EPR, 1H 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.
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发表时间: 2017-08-09
影响因子: 15
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