One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process

Sarma, B. B. ; Kim, J. ; Amsler, J. ; Agostini, G. ; Weidenthaler, C. ; Pfänder, N. ; Arenal, R. (Universidad de Zaragoza) ; Concepción, P. ; Plessow, P. ; Studt, F. ; Prieto, G.

Resumen: Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov a-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.

Idioma: Inglés

DOI: 10.1002/anie.201915255

Año: 2020

Publicado en: Angewandte Chemie (International ed.) 59 , 14 (2020), 5806-5815
ISSN: 1433-7851

Originalmente disponible en: Texto completo de la revista

Factor impacto JCR: 15.336 (2020)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 16 / 178 = 0.09 (2020) - Q1 - T1

Factor impacto SCIMAGO: 5.831 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/EC/H2020/823717/EU/Enabling Science and Technology through European Electron Microscopy/ESTEEM3
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RTI2018-096399-A-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/MAT2016-79776-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/SEV-2016-0683

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Física Materia Condensada (Dpto. Física Materia Condensa.)