title: Pulsed-EPR evidence of a manganese(II) hydroxycarbonyl intermediate in the electrocatalytic reduction of carbon dioxide by a manganese bipyridyl derivative.
abstract: 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.
authors.affiliation: Université Joseph Fourier-Grenoble1/CNRS, Département de Chimie Moléculaire UMR5250, Laboratoire de Chimie Inorganique Redox, Institut de Chimie Moléculaire de Grenoble FR-CNRS-2607, BP53, 38041 Grenoble cedex 09 (France).
authors.forename: Marc
authors.initials: M
authors.lastname: Bourrez
authors.forename: Maylis
authors.initials: M
authors.lastname: Orio
authors.forename: Florian
authors.initials: F
authors.lastname: Molton
authors.forename: Hervé
authors.initials: H
authors.lastname: Vezin
authors.forename: Carole
authors.initials: C
authors.lastname: Duboc
authors.forename: Alain
authors.initials: A
authors.lastname: Deronzier
authors.forename: Sylvie
authors.initials: S
authors.lastname: Chardon-Noblat
keywords: EPR spectroscopy; carbon dioxide; catalysis; electrocatalysis; manganese