双核[FeFe]-氢化酶模拟物的合成及电化学研究

IF 3.5 4区 化学 Q2 ELECTROCHEMISTRY
Benedikt Callies, Kai-Thorben Kuessner, Sven T. Stripp, Stephan Kupfer, Phil Köhler, Helmar Görls, Inke Siewert, Wolfgang Weigand
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引用次数: 0

摘要

本文报道了一种[FeFe]-氢化酶模拟物,该模拟物具有在配体的4位和5位上具有两个氨基的苯-1,2-二硫代酸配体。配体的合成是直接的,分两步完成。详细的研究表明,官能团在[FeFe]-氢化酶模拟物中的实现对电化学质子还原反应的结构、热力学性质和催化性能的影响微乎其微。然而,这种修饰为配体主链的各种功能化开辟了道路,例如在光电催化中的应用。电化学研究表明,最初的两个电子还原之后是醋酸的质子化,形成不对称的二铁氢化物。氢化物种类的进一步减少和质子化导致H2的形成。利用波脚分析,确定了由金属氢化物与外酸反应组成的析氢步骤的反应速率为2 × 108 s−1 m−1。然而,氢化物的形成速率常数约为4 × 104 s−1 m−1,限制了催化作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Synthesis and Electrochemical Investigations of a Binuclear [FeFe]-Hydrogenase Mimic

Synthesis and Electrochemical Investigations of a Binuclear [FeFe]-Hydrogenase Mimic

Herein, a [FeFe]-hydrogenase mimic with the benzene-1,2-dithiolato ligand bearing two amino groups in 4- and 5-position of the ligand is reported. The ligand synthesis is straight forward and accomplished in two steps. Detailed studies show that the implementation of the functional groups in the [FeFe]-hydrogenase mimic has marginal impact on the structural, thermodynamic properties, and catalytic performance in the electrochemical proton reduction reaction. However, the modification opens the way for a wide variety of functionalization in the ligand backbone, e.g., for applications in photo/electrocatalysis. Electrochemical investigations reveal that initial two electron reductions are followed by protonation by acetic acid forming an asymmetric diironhydride species. Further reduction of the hydride species and protonation leads to H2 formation. Utilizing foot of the wave analysis, a reaction rate of 2 × 108 s−1m−1 for the H2 evolution step consisting of the reaction of the metal hydride species and the external acid has been determined. However, catalysis is limited by the formation of the hydride at a rate constant of about 4 × 104 s−1m−1.

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来源期刊
ChemElectroChem
ChemElectroChem ELECTROCHEMISTRY-
CiteScore
7.90
自引率
2.50%
发文量
515
审稿时长
1.2 months
期刊介绍: ChemElectroChem is aimed to become a top-ranking electrochemistry journal for primary research papers and critical secondary information from authors across the world. The journal covers the entire scope of pure and applied electrochemistry, the latter encompassing (among others) energy applications, electrochemistry at interfaces (including surfaces), photoelectrochemistry and bioelectrochemistry.
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