The authors thank the TGE Réseau National de RPE interdisciplinaire, FR-CNRS 3443, the “Agence Nationale pour la Recherche” (grant number ANR-08-CP2D-05-01; CO2GREEN) and the Labex ARCANE (grant number ANR-11-LABX-0003-01) for financial supports. We also thank M. Stanbury for proofreading of the manuscript.
Pulsed-EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative†
Article first published online: 20 NOV 2013
Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Volume 126, Issue 1, pages 244–247, January 3, 2014
How to Cite
Bourrez, M., Orio, M., Molton, F., Vezin, H., Duboc, C., Deronzier, A. and Chardon-Noblat, S. (2014), Pulsed-EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative. Angew. Chem., 126: 244–247. doi: 10.1002/ange.201306750
- Issue published online: 23 DEC 2013
- Article first published online: 20 NOV 2013
- Manuscript Revised: 11 OCT 2013
- Manuscript Received: 1 AUG 2013
- FR-CNRS. Grant Number: ANR-08-CP2D-05-01
- Labex ARCANE. Grant Number: ANR-11-LABX-0003-01
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 Mn0 carbonyl dimer, an unexpected intermediate.