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一种非血红素过氧二铁(III)配合物,对有机底物同时表现出亲核氧化和亲电氧化作用。

A nonheme peroxo-diiron(III) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates.

作者信息

Török Patrik, Unjaroen Duenpen, Viktória Csendes Flóra, Giorgi Michel, Browne Wesley R, Kaizer József

机构信息

Research Group of Bioorganic and Biocoordination Chemistry, University of Pannonia, H-8200 Veszprém, Hungary.

Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.

出版信息

Dalton Trans. 2021 Jun 1;50(21):7181-7185. doi: 10.1039/d1dt01502h.

Abstract

The complex [FeIII2(μ-O2)(L3)4(S)2]4+ (L3 = 2-(4-thiazolyl)benzimidazole, S = solvent) forms upon reaction of [FeII(L3)2] with H2O2 and is a functional model of peroxo-diiron intermediates invoked during the catalytic cycle of oxidoreductases. The spectroscopic properties of the complex are in line with those of complexes formed with N-donor ligands. [FeIII2(μ-O2)(L3)4(S)2]4+ shows both nucleophilic (aldehydes) and electrophilic (phenol, N,N-dimethylanilines) oxidative reactivity and unusually also electron transfer oxidation.

摘要

配合物[FeIII2(μ - O2)(L3)4(S)2]4+(L3 = 2 - (4 - 噻唑基)苯并咪唑,S = 溶剂)由[FeII(L3)2]与H2O2反应形成,是氧化还原酶催化循环中涉及的过氧 - 二铁中间体的功能模型。该配合物的光谱性质与由氮供体配体形成的配合物的光谱性质一致。[FeIII2(μ - O2)(L3)4(S)2]4+既表现出亲核(醛)和亲电(苯酚、N,N - 二甲基苯胺)氧化反应性,而且还表现出异常的电子转移氧化反应性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d463/8168641/0cd434b26a17/d1dt01502h-s1.jpg

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