One of the most appealing research areas is the mechanistic understanding of multi-electron multi-proton processes, being a central part in the activation of small molecules such as CO2 or reduction of water to H2. In this line, we have discovered that cobalt coordination complexes based on the tacn moiety are highly efficient homogeneous catalysts for the reduction of water, organic substrates and CO2. In particular, we have developed a methodology for a light-driven reduction of ketones, aldehydes and olefins, using water/electron donor as a source of hydrogen with an unique selectivity towards aromatic ketones. Here we will present the characterization of new key intermediates of these transformations and the influence of the non-innocent nature of the ligand. To gain insight into the mechanism we have carried out a detailed study by kinetics, spectroscopic monitoring of intermediates, kinetic isotopic effects, isotopic labelling, electronic effects and DFT calculations. The scope of the system and mechanistic aspects will be discussed.

Catalytic light-driven reductive transformations mediated by cobalt complexes

253rd National Meeting (2017)

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