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Abstract

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.