A Homobimetallic Frustrated Lewis Pair Cobalt Catalyst for the Methanolysis of Hydrosilanes

Luque-Gómez, Ana ; Barrena-Espés, Daniel ; García-Orduña, Pilar ; Pérez-García, Andrea (Universidad de Zaragoza) ; Casado, Miguel A. (Universidad de Zaragoza) ; Munarriz, Julen (Universidad de Zaragoza) ; Iglesias, Manuel

Resumen: The bimetallic Co(I)/Co(–I) complex [Co(CO)2(κ3‐P,N,P‐PNHP)][Co(CO)4] (1) has shown excellent activities in the methanolysis of hydrosilanes, surpassing the related bimetallic Co(I)/Co(–I) complex [Co(CO)(PMe2Ph)(κ3‐P,N,P‐PNHP)][Co(CO)4] (2), the Co(II) complex [Co(Cl)2(κ3‐P,N,P‐PNHP)] (3), and the Co(I) complex [Co(CO)2(κ3‐P,N,P‐PNHP)]Cl (4). A comprehensive DFT study of the plausible reaction mechanisms indicates that the enhanced activity of 1 can be attributed to the presence of the [Co(CO)4]– anion, which enables a frustrated Lewis pair (FLP) mechanism that provides a low energy pathway for the heterolytic splitting of the Si─H bond. The reaction mechanism entails the coordination of the hydrosilane to the Co(I) center upon decoordination of the amine functionality of the PNHP ligand, followed by heterolytic splitting of the Si─H bond with the participation of the Co(I) and Co(–I) centers. Then, the PhSiH2 group at the Co(–I) center is transferred to the oxygen atom of a methanol molecule, which affords the [H2SiPh(HOMe)]+ cation, regenerating the [Co(CO)4]– species. [H2SiPh(HOMe)]+ protonates the hydride at the Co(I) center, leading to the formation of H2 and the corresponding silyl ether. Alternative reaction pathways, including alternative ionic mechanisms or NH‐assisted bifunctional mechanisms, result in higher activation energies.

Idioma: Inglés

DOI: 10.1002/anie.202513522

Año: 2025

Publicado en: Angewandte Chemie (International ed.) (2025), e202513522 [11 pp.]
ISSN: 1433-7851

Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PRE2019-087598
Financiación: info:eu-repo/grantAgreement/ES/UZ/JIUZ-2023-CIE-10

Tipo y forma: Artículo (Versión definitiva)

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