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-RuO (x) 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 RuO (x) sites and react with the nucleophile to achieve the selenylation of heterocycles.
