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: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes.
Exportado de SIDERAL (2025-10-17-14:14:12)
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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: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. Exportado de SIDERAL (2025-10-17-14:14:12)
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Record created 2025-08-26, last modified 2025-10-17