CO2 / 13CO2 Dynamic Exchange in the Formate Complex [(2,9-(tBu) 2-phen)Cu(O2CH)] and Its Catalytic Activity in the Dehydrogenation of Formic Acid - CEA - Commissariat à l’énergie atomique et aux énergies alternatives Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2023

CO2 / 13CO2 Dynamic Exchange in the Formate Complex [(2,9-(tBu) 2-phen)Cu(O2CH)] and Its Catalytic Activity in the Dehydrogenation of Formic Acid

Résumé

Formate complexes of copper(I) are rare. We report here the synthesis, characterization, and crystal structure of the simple tricoordinate [(phen*)Cu I (K11-O2CH)] (1) supported with the bulky phenanthroline ligand 2,9-di-terbutyl-1,10-phenanthroline (phen*). Complex 1 decarboxylates at 100°C to give H2 and Cu(0) deposit with free phen*. To ensure that the degradation process goes through the hypothetical hydride [(phen*)CuH], Lewis acidic boron BR3 compounds (R = C6F5, Et) or organic scavengers have been introduced to trap it. In most case degradation occurs except with B(C6F5)3 that give the cationic complex [{(phen*)Cu}2(µ-HCO2)][(HCO2)B(C6F5)3] (2) which has been crystallized. While 1 does not react with CS2 when heated, it undergoes under 1 atm of 13 CO2, a dynamic decarboxylation/carboxylation process that indicates transient formation of the hydride. The catalytic activity of complex 1 in the dehydrogenation of formic acid is revealed.
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cea-04440597 , version 1 (06-02-2024)

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Paternité - Pas d'utilisation commerciale - Pas de modification

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Kieu Phung, Pierre Thuéry, Jean-Claude Berthet, Thibault Cantat. CO2 / 13CO2 Dynamic Exchange in the Formate Complex [(2,9-(tBu) 2-phen)Cu(O2CH)] and Its Catalytic Activity in the Dehydrogenation of Formic Acid. Organometallics, 2023, 42 (23), pp.3357-3365. ⟨10.1021/acs.organomet.3c00302⟩. ⟨cea-04440597⟩
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