Electrochemical Formation and Reactivity of a Mn‐Peroxo Complex Bearing an Amido N5 Ligand
Electrochemical Formation and Reactivity of a Mn‐Peroxo Complex Bearing an Amido N5 Ligand
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带有氨基 N5 配体的 Mn-Peroxo 配合物的电化学形成和反应活性
DOI：
10.1002/celc.202200112
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发表时间：
2022
期刊：
影响因子：
4
通讯作者：
Anxolabéhère‐Mallart, Elodie
中科院分区：
文献类型：
--
作者：
Massie, Allyssa A.;Kostopoulos, Nikolaos;Grotemeyer, Elizabeth N.;Noël, Jean‐Marc;Jackson, Timothy A.;Anxolabéhère‐Mallart, Elodie
本文首次报道了以dpaq为配体（dpaq=2‐（双（吡啶‐2‐甲基）氨基）‐N‐（喹啉‐8‐基）乙酰胺）为载体的单核MnIII(OO)（过氧）配合物的电化学生成及其反应活性inN，N‐二甲基甲酰胺。采用低温电子吸收光谱电化学实验研究了MnIII(dpaq)（OO）配合物的形成。结合循环伏安法和模拟分析了MnIII(dpaq)（OO）配合物的还原。基于CV数据提出了MnII(dpaq)（OOH）配合物的参与，并通过DFT计算得到了证实。
Herein we report the electrochemical generation of a mononuclear MnIII(OO) (peroxo) complex supported on a dpaq ligand (dpaq=2‐(bis(pyridin‐2‐ylmethyl)amino)‐N‐(quinolin‐8‐yl)acetamide) for the first time, and its reactivity inN,N‐dimethylformamide. The formation of the MnIII(dpaq)(OO) complex is probed by low temperature electronic absorption spectro‐electrochemistry experiments. An analysis of the reduction of the MnIII(dpaq)(OO) complex is carried out combining cyclic voltammetry and simulations. The involvement of a MnII(dpaq)(OOH) complex is proposed based on CV data and is corroborated by DFT computations.