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首页> 外文期刊>Chemistry: A European journal >Influence of the Dithiolate Bridge on the Oxidative Processes of Diiron Models Related to the Active Site of [FeFe] Hydrogenases
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Influence of the Dithiolate Bridge on the Oxidative Processes of Diiron Models Related to the Active Site of [FeFe] Hydrogenases

机译：二硫酸盐桥对氢氢酶活性位点相关的Dion模型氧化过程的影响

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摘要

Electrochemical studies of [Fe_2(CO)_4(κ~2-dmpe)(m-dithiolate)] (dithiolate=adt~(Bn), pdt) and density functional theory (DFT) calculations reveal the striking influence of an amine functionality in the dithiolate bridge on their oxidative properties. [Fe_2(CO)_4(κ~2-dmpe)(m-adt~(Bn))] (1) undergoes two one-electron oxidation steps, with the first being partially reversible and the second irreversible. When the adt~(Bn) bridge is replaced with pdt, a shift of 60 mV towards more positive potentials is observed for the first oxidation whereas 290 mV separate the oxidation potentials of the two cations. Under CO, oxidation of azadithiolate compound 1 occurs according to an ECE process whereas an EC mechanism takes place for the propanedithiolate species 2. The dication species [1-CO]~(2+) resulting from the two-electron oxidation of 1 has been spectroscopically and structurally characterized. The molecular details underlying the reactivity of oxidized species have been explored by DFT calculations. The differences in the behaviors of 1 and 2 are mainly due to the presence, or not, of favored interactions between the dithiolate bridge and the diiron site depending on the redox states, FeIFe~(II) or Fe~(II)Fe~(II), of the complexes.
机译：[Fe_2（CO）_4（κ〜2-DMPE）（M-DITHIOLATE）]的电化学研究（二硫酸盐= ADT〜（BN），PDT）和密度泛函（DFT）计算揭示了胺功能的罢工影响氧化性能的二硫酸盐桥。 [Fe_2（CO）_4（κ〜2-DMPE）（M-ADT〜（BN））]（1）经历两个单电子氧化步骤，首先是部分可逆的，第二不可逆。当用PDT代替ADT〜（BN）桥时，对于第一氧化，观察到60mV朝向更大的正电位的偏移，而第290 MV分离两个阳离子的氧化电位。在CO下，根据ECE方法，发生异硫酸盐化合物1的氧化，而EC机理发生针对丙酸二盐物质2。由二电子氧化1的二氧化碳物质[1-CO]〜（2+）已成为光谱和结构性地表征。通过DFT计算探讨了氧化物种反应性的分子细节。 1和2的行为的差异主要是由于在氧化还原态，Feife〜（ii）或Fe〜（II）Fe〜（ II），复合物。

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  • 来源
    《Chemistry: A European journal》 |2017年第18期|共9页
  • 作者

    Federica Arrigoni; Salma Mohamed Bouh; Luca De Gioia; Catherine Elleouet; Fran?ois Y. Pétillon; Philippe Schollhammer; Giuseppe Zampella;

  • 作者单位

    Department of Biotechnology and Bioscience University of Milano-Bicocca Piazza della Scienza 2 20126 Milan (Italy);

    UMR CNRS 6521 Chimie Electrochimie Moléculaires et Chimie Analytique Université de Bretagne Occidentale UFR Sciences et Techniques 6 Avenue Victor le Gorgeu CS 93837 29238 Brest-Cedex 3 (France);

    Department of Biotechnology and Bioscience University of Milano-Bicocca Piazza della Scienza 2 20126 Milan (Italy);

    UMR CNRS 6521 Chimie Electrochimie Moléculaires et Chimie Analytique Université de Bretagne Occidentale UFR Sciences et Techniques 6 Avenue Victor le Gorgeu CS 93837 29238 Brest-Cedex 3 (France);

    UMR CNRS 6521 Chimie Electrochimie Moléculaires et Chimie Analytique Université de Bretagne Occidentale UFR Sciences et Techniques 6 Avenue Victor le Gorgeu CS 93837 29238 Brest-Cedex 3 (France);

    UMR CNRS 6521 Chimie Electrochimie Moléculaires et Chimie Analytique Université de Bretagne Occidentale UFR Sciences et Techniques 6 Avenue Victor le Gorgeu CS 93837 29238 Brest-Cedex 3 (France);

    Department of Biotechnology and Bioscience University of Milano-Bicocca Piazza della Scienza 2 20126 Milan (Italy);

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 应用化学;
  • 关键词

    bridging ligands; density functional theory; electrochemistry; enzyme models; oxidation;

    机译：桥接配体;密度函数理论;电化学;酶模型;氧化;

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