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

[EN] 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 Ru-1/CeO2 and Rh-1/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 alpha-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.X-ray absorption experiments were performed at the ALBA Synchrotron Light Source (Spain), experiments 2018082961 and 2019023278. L. Simonelli and C. Marini (CLAESSALBA beamline) are thanked for beamline setup. E. Andres, M. E. Martinez, M. Garcia, and I. Lopez (ITQ), are acknowledged for their assistance with XAS experiments. J. Buscher, J. Ternedien, B. Spliethoff, and C. Wirtz (MPI-KOFO) are acknowledged for the performance of XPS, XRD, BF-TEM and 2H NMR experiments, respectively. I. C. de Freitas (MPIKOFO) is thanked for assistance with Raman spectroscopy. J. M. Salas (ITQ) is gratefully acknowledged for his contribution to CO-FTIR experiments. J. J. Barnes and Shell (Amsterdam) are acknowledged for kindly providing an industrial olefin mixture as feed. Authors are thankful to F. Schuth for the provision of lab space and continued support. Part of the HRSTEM and EDX-STEM studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. R.A. gratefully acknowledges the support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project grant MAT2016-79776-P (AEI/FEDER, UE) and from the European Union H2020 programs "ESTEEM3" (823717). The authors acknowledge support by the state of Baden-Wurttemberg through bwHPC (bwUnicluster and JUSTUS, RV bw17D01), by the GRK 2450 and by the Helmholtz Association. This research received funding from the Max Planck Society, and the Fonds der Chemische Industrie of Germany. Funding from the Spanish Ministry of Science, Innovation and Universities (Severo Ochoa program SEV-2016-0683 and grant RTI2018096399-A-I00) is also acknowledged. B.B.S. acknowledges the Alexander von Humboldt Foundation for a postdoctoral scholarship. Open Access funding is provided by the Max Planck Society.Sarma, BB.; Kim, J.; Amsler, J.; Agostini, G.; Weidenthaler, C.; Pfaender, N.; Arenal, R.... (2020). One Pot Cooperation of Single Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization - Hydrosilylation Process. Angewandte Chemie International Edition. 59(14):5806-5815. https://doi.org/10.1002/anie.201915255580658155914Liang, S., Hao, C., & Shi, Y. (2015). The Power of Single-Atom Catalysis. ChemCatChem, 7(17), 2559-2567. doi:10.1002/cctc.201500363Liu, J. (2016). Catalysis by Supported Single Metal Atoms. 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