Alternative Conceptual Approach to the Design of Bifunctional Catalysts: An Osmium Germylene System for the Dehydrogenation of Formic Acid

Buil, M.L. (Universidad de Zaragoza) ; Cabeza, J.A. ; Esteruelas, M.A. ; Izquierdo, S. (Universidad de Zaragoza) ; Laglera-Gándara, C.J. ; Iglesias Nicasio, A. ; Oñate, E.

Resumen: The reaction of the hexahydride OsH6(PiPr3)2 with a P, Ge, P-germylene-diphosphine affords an osmium tetrahydride derivative bearing a Ge, P-chelate, which arises from the hydrogenolysis of a P-C(sp3) bond. This Os(IV)-Ge(II) compound is a pioneering example of a bifunctional catalyst based on the coordination of a s-donor acid, which is active in the dehydrogenation of formic acid to H2 and CO2. The kinetics of the dehydrogenation, the characterization of the resting state of the catalysis, and DFT calculations point out that the hydrogen formation (the fast stage) exclusively occurs on the coordination sphere of the basic metal center, whereas both the metal center and the s-donor Lewis acid cooperatively participate in the CO2 release (the rate-determining step). During the process, the formate group pivots around the germanium to approach its hydrogen atom to the osmium center, which allows its transfer to the metal and the CO2 release.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.1c02893

Año: 2021

Publicado en: Inorganic Chemistry 60, 21 (2021), 16860-16870
ISSN: 0020-1669

Factor impacto JCR: 5.436 (2021)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 5 / 46 = 0.109 (2021) - Q1 - T1

Factor impacto SCIMAGO: 1.121 - Inorganic Chemistry (Q1) - Chemistry (miscellaneous) (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/FEDER E06-20R
Financiación: info:eu-repo/grantAgreement/ES/DGA/LMP148-18
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RED2018-102387-T

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)