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Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

revised on 02.02.2021, 15:26 and posted on 03.02.2021, 10:29 by Nicolas Lentz, Alicia Aloisi, Pierre Thuéry, Emmanuel Nicolas, Thibault Cantat
The reversible storage of hydrogen through the intermediate formation of Formic Acid (FA) is a promising solution to its safe transport and distribution. However, the common necessity of using bases or additives in the catalytic dehydrogenation of FA is a limitation. In this context, two new cobalt complexes (1 and 2) were synthesized with a pincer PP(NH)P ligand containing a phosphoramine moiety. Their reaction with an excess FA yields a cobalt(I)-hydride complex (3). We report here the unprecedented catalytic activity of 3 in the dehydrogenation of FA, with a turnover frequency (TOF) of 4000 h-1 and a turnover number (TON) of 454, without the need for bases or additives. A mechanistic study reveals that the ligand has a non-innocent behaviour due to intermolecular hydrogen bonding, which is influenced by the concentration of formic acid




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Université Paris-Saclay, CEA, CNRS, NIMBE



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no conflict of interest