Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

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...

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Bibliographic Details
Published inOrganometallics Vol. 40; no. 5; pp. 565 - 569
Main Authors Lentz, Nicolas, Aloisi, Alicia, Thuéry, Pierre, Nicolas, Emmanuel, Cantat, Thibault
Format Journal Article
LanguageEnglish
Published American Chemical Society 08.03.2021
Subjects
Catalysis
Chemical Sciences
formic acid
catalysis
cobalt
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Summary: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 67 min–1 measured in the first minute and a turnover number (TON) of 454, without the need for bases or additives. A mechanistic study reveals the existence of ligand–metal cooperativity with intermolecular hydrogen bonding, also influenced by the concentration of formic acid.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.0c00777