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The transition from homogeneous to heterogeneous synthetic chemistry enabled by nanocatalysts necessitates investigations of the reaction mechanism and structure-activity relationships for inorganic nanoparticles and organic substrates. Herein, we report that hydrothermally synthesized ruthenium nanoparticles performed differently in the Se–Se bond activation and selenylation of heterocycles, exhibiting a volcano-shaped relationship between catalytic activity and composition. A synergistic effect was observed for Ru-RuOx nanocatalysts, with numerous characterizations and density functional theory (DFT) calculations suggesting that a PhSeSePh molecule can initially be adsorbed on the metallic Ru sites and cleaved into two PhSe* species, which subsequently migrate to RuOx sites and react with the nucleophile to achieve the selenylation of heterocycles.
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