Electro and photoreduction of CO2 driven by manganese-carbonyl molecular catalysts

Manganese carbonyl complexes have become popular homogeneous catalysts for carbon dioxide electroor photoreduction since the beginning of the 2010s. This article presents a comprehensive survey of all the Mn carbonyl systems reported during the last decade as being active catalysts for CO2 reduction, with a comparison of their activity, stability and selectivity under electroreduction and, for some of them, photoreduction conditions. The development of in situ spectroelectrochemical techniques, often backed by OFT calculations, has enabled gaining more insight into the associated catalytic mechanisms and reaction intermediates. Though manganese tricarbonyl compounds featuring a bipyridine derivative have been by far the most studied, alternative Mn coordination spheres have recently been explored, opening a way towards new families of potential catalysts for homogeneous and heterogeneous CO2 reduction. (C) 2018 Elsevier B.V. All rights reserved.