162404 20251017144601.0 doi 10.1002/anie.202513522 sideral 144950 ART-2025-144950 eng Luque-Gómez, Ana A Homobimetallic Frustrated Lewis Pair Cobalt Catalyst for the Methanolysis of Hydrosilanes 2025 Access copy available to the general public Unrestricted 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. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00 info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00 info:eu-repo/grantAgreement/ES/MICINN/PRE2019-087598 info:eu-repo/grantAgreement/ES/UZ/JIUZ-2023-CIE-10 info:eu-repo/semantics/openAccess by-nc https://creativecommons.org/licenses/by-nc/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Barrena-Espés, Daniel García-Orduña, Pilar (orcid)0000-0002-7063-1292 Pérez-García, Andrea Universidad de Zaragoza Casado, Miguel A. Universidad de Zaragoza (orcid)0000-0003-1707-3022 Munarriz, Julen Universidad de Zaragoza (orcid)0000-0001-6089-6126 Iglesias, Manuel (orcid)0000-0003-3144-5320 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física (2025), e202513522 [11 pp.] Angew. Chem. (Int. ed.) Angewandte Chemie (International ed.) 1433-7851 2029350 http://zaguan.unizar.es/record/162404/files/texto_completo.pdf Versión publicada 2993256 http://zaguan.unizar.es/record/162404/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:162404 articulos driver 2025-10-17-14:14:12 ARTICLE