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
Revue
Angewandte Chemie
Volume
126
Pagination
244-247
Soumis le 17 mai 2018