{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,17]],"date-time":"2026-07-17T17:05:15Z","timestamp":1784307915596,"version":"3.55.0"},"reference-count":80,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2025,7,17]],"date-time":"2025-07-17T00:00:00Z","timestamp":1752710400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"},{"start":{"date-parts":[[2025,7,17]],"date-time":"2025-07-17T00:00:00Z","timestamp":1752710400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2025,9,1]]},"abstract":"Abstract<\/jats:title>\n \n The bimetallic Co(I)\/Co(\u2013I) complex [Co(CO)\n 2<\/jats:sub>\n (\u03ba\n 3<\/jats:sup>\n \u2010\n P<\/jats:italic>\n ,\n N<\/jats:italic>\n ,\n P<\/jats:italic>\n \u2010PN\n H<\/jats:sup>\n P)][Co(CO)\n 4<\/jats:sub>\n ] (\n 1<\/jats:bold>\n ) has shown excellent activities in the methanolysis of hydrosilanes, surpassing the related bimetallic Co(I)\/Co(\u2013I) complex [Co(CO)(PMe\n 2<\/jats:sub>\n Ph)(\u03ba\n 3<\/jats:sup>\n \u2010\n P<\/jats:italic>\n ,\n N<\/jats:italic>\n ,\n P<\/jats:italic>\n \u2010PN\n H<\/jats:sup>\n P)][Co(CO)\n 4<\/jats:sub>\n ] (\n 2<\/jats:bold>\n ), the Co(II) complex [Co(Cl)\n 2<\/jats:sub>\n (\u03ba\n 3<\/jats:sup>\n \u2010\n P<\/jats:italic>\n ,\n N<\/jats:italic>\n ,\n P<\/jats:italic>\n \u2010PN\n H<\/jats:sup>\n P)] (\n 3<\/jats:bold>\n ), and the Co(I) complex [Co(CO)\n 2<\/jats:sub>\n (\u03ba\n 3<\/jats:sup>\n \u2010\n P<\/jats:italic>\n ,\n N<\/jats:italic>\n ,\n P<\/jats:italic>\n \u2010PN\n H<\/jats:sup>\n P)]Cl (\n 4<\/jats:bold>\n ). A comprehensive DFT study of the plausible reaction mechanisms indicates that the enhanced activity of\n 1<\/jats:bold>\n can be attributed to the presence of the [Co(CO)\n 4<\/jats:sub>\n ]\n \u2013<\/jats:sup>\n anion, which enables a frustrated Lewis pair (FLP) mechanism that provides a low energy pathway for the heterolytic splitting of the Si\u2500H bond. The reaction mechanism entails the coordination of the hydrosilane to the Co(I) center upon decoordination of the amine functionality of the PN\n H<\/jats:sup>\n P ligand, followed by heterolytic splitting of the Si\u2500H bond with the participation of the Co(I) and Co(\u2013I) centers. Then, the PhSiH\n 2<\/jats:sub>\n group at the Co(\u2013I) center is transferred to the oxygen atom of a methanol molecule, which affords the [H\n 2<\/jats:sub>\n SiPh(HOMe)]\n +<\/jats:sup>\n cation, regenerating the [Co(CO)\n 4<\/jats:sub>\n ]\n \u2013<\/jats:sup>\n species. [H\n 2<\/jats:sub>\n SiPh(HOMe)]\n +<\/jats:sup>\n protonates the hydride at the Co(I) center, leading to the formation of H\n 2<\/jats:sub>\n and the corresponding silyl ether. Alternative reaction pathways, including alternative ionic mechanisms or NH\u2010assisted bifunctional mechanisms, result in higher activation energies.\n <\/jats:p>","DOI":"10.1002\/anie.202513522","type":"journal-article","created":{"date-parts":[[2025,7,3]],"date-time":"2025-07-03T07:01:58Z","timestamp":1751526118000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["A Homobimetallic Frustrated Lewis Pair Cobalt Catalyst for the Methanolysis of Hydrosilanes"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0132-6577","authenticated-orcid":false,"given":"Ana","family":"Luque\u2010G\u00f3mez","sequence":"first","affiliation":[{"name":"Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea CSIC\u2010Universidad de Zaragoza C\/Pedro Cerbuna 12, Facultad de Ciencias Zaragoza 50009 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6326-9611","authenticated-orcid":false,"given":"Daniel","family":"Barrena\u2010Esp\u00e9s","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica y Anal\u00edtica Universidad de Oviedo Avda. 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