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 Mn0 carbonyl dimer, an unexpected intermediate.
Références
- Titre
- Pulsed‐EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative
- Type de publication
- Article de revue
- Année de publication
- 2014
- Auteurs
- Marc, Bourrez, Maylis Orio, Florian Molton, Hervé Vezin, Carole Duboc, Alain Deronzier, and Sylvie Chardon‐Noblat
- Revue
- Angewandte Chemie
- Volume
- 126
- Pagination
- 244-247
Soumis le 17 mai 2018