Pulsed-EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative

被引：115

作者：

Bourrez, Marc ^{[1
]}

Orio, Maylis ^{[2
]}

Molton, Florian ^{[1
]}

Vezin, Herve ^{[1
,2
]}

Duboc, Carole ^{[1
]}

Deronzier, Alain ^{[1
]}

Chardon-Noblat, Sylvie ^{[1
]}

机构：

[1] Univ Grenoble 1, CNRS, Inst Chim Mol Grenoble FR CNRS 2607, Dept Chim Mol UMR5250,Lab Chim Inorgan Redox, F-38041 Grenoble 09, France

[2] Univ Lille 1, Lab Spectrochim Infrarouge & Raman, UMR CNRS 8516, F-59655 Villeneuve Dascq, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 01期

关键词：

carbon dioxide; catalysis; electrocatalysis; EPR spectroscopy; manganese; ELECTROCHEMICAL REDUCTION; RHENIUM(I) COMPLEXES; CHARGE-TRANSFER; CO2; CATALYSIS; ELECTROREDUCTION; 2,2'-BIPYRIDINE; CONVERSION; RELEVANT; ELECTRON;

D O I：

10.1002/anie.201306750

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A key intermediate in the electroconversion of carbon dioxide to carbon monoxide, catalyzed by a manganese tris(carbonyl) complex, is characterized. Different catalytic pathways and their potential reaction mechanisms are investigated using a large range of experimental and computational techniques. Sophisticated spectroscopic methods including UV/Vis absorption and pulsed-EPR techniques (2P-ESEEM and HYSCORE) were combined together with DFT calculations to successfully identify a key intermediate in the catalytic cycle of CO2 reduction. The results directly show the formation of a metal-carboxylic acid-CO2 adduct after oxidative addition of CO2 and H+ to a Mn-0 carbonyl dimer, an unexpected intermediate.

引用

页码：240 / 243

页数：4

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