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 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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Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

10.26434/chemrxiv.12901925.v3 ◽

2021 ◽

Author(s):

Nicolas Lentz ◽

Alicia Aloisi ◽

Pierre Thuéry ◽

Emmanuel Nicolas ◽

Thibault Cantat

Keyword(s):

Formic Acid ◽

Cobalt Complex ◽

Intermediate Formation ◽

Mechanistic Study ◽

Catalytic Dehydrogenation ◽

Turnover Number ◽

Promising Solution ◽

The Common ◽

Safe Transport ◽

Formic Acid Dehydrogenation

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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Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

10.26434/chemrxiv.12901925.v1 ◽

2020 ◽

Author(s):

Nicolas Lentz ◽

Alicia Aloisi ◽

Pierre Thuéry ◽

Emmanuel Nicolas ◽

Thibault Cantat

Keyword(s):

Formic Acid ◽

Cobalt Complex ◽

Intermediate Formation ◽

Mechanistic Study ◽

Catalytic Dehydrogenation ◽

Turnover Number ◽

Promising Solution ◽

The Common ◽

Safe Transport ◽

Formic Acid Dehydrogenation

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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Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

Organometallics ◽

10.1021/acs.organomet.0c00777 ◽

2021 ◽

Author(s):

Nicolas Lentz ◽

Alicia Aloisi ◽

Pierre Thuéry ◽

Emmanuel Nicolas ◽

Thibault Cantat

Keyword(s):

Formic Acid ◽

Cobalt Complex ◽

Formic Acid Dehydrogenation

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Structural analysis of transient reaction intermediate in formic acid dehydrogenation catalysis using two-dimensional IR spectroscopy

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1809342115 ◽

2018 ◽

Vol 115 (49) ◽

pp. 12395-12400 ◽

Cited By ~ 9

Author(s):

Yufan Zhang ◽

Xin Chen ◽

Bin Zheng ◽

Xunmin Guo ◽

Yupeng Pan ◽

...

Keyword(s):

Ir Spectroscopy ◽

Formic Acid ◽

Spectroscopic Studies ◽

Turnover Number ◽

Ru Catalyst ◽

2D Ir ◽

Catalytically Active ◽

Complex Features ◽

Formic Acid Dehydrogenation ◽

Formate Intermediate

The molecular structure of a catalytically active key intermediate is determined in solution by employing 2D IR spectroscopy measuring vibrational cross-angles. The formate intermediate (2) in the formic acid dehydrogenation reaction catalyzed by a phosphorus–nitrogen PN3P–Ru catalyst is elucidated. Our spectroscopic studies show that the complex features a formate ion directly attached to the Ru center as a ligand, and a proton added to the imine arm of the dearomatized PN3P* ligand. During the catalytic process, the imine arms are not only reversibly protonated and deprotonated, but also interacting with the protic substrate molecules, effectively serving as the local proton buffer to offer remarkable stability with a turnover number (TON) over one million.

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Reversible cyclometalation at RhI as a motif for metal–ligand bifunctional bond activation and base-free formic acid dehydrogenation

Catalysis Science & Technology ◽

10.1039/c5cy01505g ◽

2016 ◽

Vol 6 (5) ◽

pp. 1320-1327 ◽

Cited By ~ 33

Author(s):

L. S. Jongbloed ◽

B. de Bruin ◽

J. N. H. Reek ◽

M. Lutz ◽

J. I. van der Vlugt

Keyword(s):

Formic Acid ◽

Computational Methods ◽

Bond Activation ◽

Catalytic Dehydrogenation ◽

Formic Acid Dehydrogenation ◽

Metal Ligand

The first example of base-free catalytic dehydrogenation of formic acid using reversible cyclometalation at Rh(i) is discussed, using a combination of experimental and computational methods.

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