000162404 001__ 162404
000162404 005__ 20251017144601.0
000162404 0247_ $$2doi$$a10.1002/anie.202513522
000162404 0248_ $$2sideral$$a144950
000162404 037__ $$aART-2025-144950
000162404 041__ $$aeng
000162404 100__ $$aLuque-Gómez, Ana
000162404 245__ $$aA Homobimetallic Frustrated Lewis Pair Cobalt Catalyst for the Methanolysis of Hydrosilanes
000162404 260__ $$c2025
000162404 5060_ $$aAccess copy available to the general public$$fUnrestricted
000162404 5203_ $$aThe 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.
000162404 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PRE2019-087598$$9info:eu-repo/grantAgreement/ES/UZ/JIUZ-2023-CIE-10
000162404 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttps://creativecommons.org/licenses/by-nc/4.0/deed.es
000162404 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000162404 700__ $$aBarrena-Espés, Daniel
000162404 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000162404 700__ $$aPérez-García, Andrea$$uUniversidad de Zaragoza
000162404 700__ $$0(orcid)0000-0003-1707-3022$$aCasado, Miguel A.$$uUniversidad de Zaragoza
000162404 700__ $$0(orcid)0000-0001-6089-6126$$aMunarriz, Julen$$uUniversidad de Zaragoza
000162404 700__ $$0(orcid)0000-0003-3144-5320$$aIglesias, Manuel
000162404 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000162404 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000162404 773__ $$g(2025), e202513522 [11 pp.]$$pAngew. Chem. (Int. ed.)$$tAngewandte Chemie (International ed.)$$x1433-7851
000162404 8564_ $$s2029350$$uhttps://zaguan.unizar.es/record/162404/files/texto_completo.pdf$$yVersión publicada
000162404 8564_ $$s2993256$$uhttps://zaguan.unizar.es/record/162404/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000162404 909CO $$ooai:zaguan.unizar.es:162404$$particulos$$pdriver
000162404 951__ $$a2025-10-17-14:14:12
000162404 980__ $$aARTICLE