Hemilability-controlled reactivity and hydride-mediated activation in Mn(I)-catalysed dehydrogenative Si–O bond formation

García-Abellán, Susana ; Gonzalo, Jorge (Universidad de Zaragoza) ; Pérez-García, Andrea ; Casado, Miguel A. (Universidad de Zaragoza) ; García-Orduña, Pilar ; Passarelli, Vincenzo ; Munárriz, Julen (Universidad de Zaragoza) ; Iglesias, Manuel

Resumen: Manganese(I) complexes supported by hemilabile P-N ligands based on a 1,2,3-triazole scaffold have been synthesized and evaluated as catalysts for the dehydrogenative coupling of hydrosilanes with hydroxyl compounds. Structural and spectroscopic studies, including single-crystal X-ray diffraction, confirmed the bidentate coordination of these ligands in complexes 1–5. Catalytic tests demonstrated that the ligand identity has a pronounced effect on the activity, with more labile triazole moieties showing superior performance. Notably, the use of LiHBEt3 (1:1 M ratio with 1) enabled in situ generation of a manganese hydride species, significantly enhancing the reactivity in the methanolysis of hydrosilanes, where turnover frequencies above 45,000 h−1 were achieved. DFT calculations suggest that the reaction proceeds via a concerted pathway requiring triazole moiety dissociation, providing a mechanistic basis for the role of ligand hemilability in the activation of the hydrosilane.

Idioma: Inglés

DOI: 10.1016/j.jcat.2026.116954

Año: 2026

Publicado en: Journal of Catalysis 460 (2026), 116954 [12 pp.]
ISSN: 0021-9517

Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIU/PID2024-159030NA-I00
Financiación: info:eu-repo/grantAgreement/ES/MICIU/PID2021-126212OB-I00

Tipo y forma: Artículo (Versión definitiva)

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