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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Published in | Organometallics Vol. 40; no. 5; pp. 565 - 569 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
08.03.2021
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Subjects | |
Online Access | Get full text |
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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. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/acs.organomet.0c00777 |