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在氧气存在下对一种非血红素铁（II）配合物的电化学研究。对铁（II）中心氧的还原活化的见解。

Electrochemical study of a nonheme Fe(ii) complex in the presence of dioxygen. Insights into the reductive activation of O at Fe(ii) centers.

作者信息

Ségaud Nathalie, Anxolabéhère-Mallart Elodie, Sénéchal-David Katell, Acosta-Rueda Laura, Robert Marc, Banse Frédéric

机构信息

Institut de Chimie Moléculaire et des Matériaux d'Orsay , UMR CNRS 8182 , Université Paris Sud , F-91405 Orsay Cedex , France . Email:

Laboratoire d'Electrochimie Moléculaire , Université Paris Diderot , Sorbonne Paris Cité , F-75205 PARIS CEDEX 13 , France . Email:

出版信息

Chem Sci. 2015 Jan 1;6(1):639-647. doi: 10.1039/c4sc01891e. Epub 2014 Sep 16.

DOI:10.1039/c4sc01891e
PMID:28936313
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5588783/
Abstract

Recent efforts to model the reactivity of iron oxygenases have led to the generation of nonheme Fe(OOH) and Fe(O) intermediates from Fe complexes and O but using different cofactors. This diversity emphasizes the rich chemistry of nonheme Fe(ii) complexes with dioxygen. We report an original mechanistic study of the reaction of [(TPEN)Fe] with O carried out by cyclic voltammetry. From this Fe precursor, reaction intermediates such as [(TPEN)Fe(O)], [(TPEN)Fe(OOH)] and [(TPEN)Fe(OO)] have been chemically generated in high yield, and characterized electrochemically. These electrochemical data have been used to analyse and perform simulation of the cyclic voltammograms of [(TPEN)Fe] in the presence of O. Thus, several important mechanistic informations on this reaction have been obtained. An unfavourable chemical equilibrium between O and the Fe complex occurs that leads to the Fe-peroxo complex upon reduction, similarly to heme enzymes such as P450. However, unlike in heme systems, further reduction of this latter intermediate does not result in O-O bond cleavage.

摘要

近期对铁加氧酶反应活性进行建模的努力，已通过使用不同的辅因子，从铁配合物和氧气中生成了非血红素铁（氧代羟基）和铁（氧）中间体。这种多样性凸显了非血红素铁（II）配合物与双氧反应丰富的化学性质。我们报道了一项通过循环伏安法对[(TPEN)Fe]与氧气反应进行的原创机理研究。从这种铁前体出发，已高产率地化学生成了诸如[(TPEN)Fe(O)]、[(TPEN)Fe(OOH)]和[(TPEN)Fe(OO)]等反应中间体，并通过电化学方法对其进行了表征。这些电化学数据已用于分析和模拟[(TPEN)Fe]在有氧气存在时的循环伏安图。因此，已获得了关于该反应的若干重要机理信息。氧气与铁配合物之间存在不利的化学平衡，这导致在还原时生成铁过氧配合物，类似于诸如P450等血红素酶。然而，与血红素体系不同的是，后一种中间体的进一步还原并不会导致O - O键的断裂。

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