Well-defined coordination environment breaks the bottleneck of organic synthesis: Single-atom palladium catalyzed hydrosilylation of internal alkynes

Single-atom site (SAS) catalysts have attracted considerable attention due to their excellent performance. However, most of the current research models of SAS catalysts are based on inorganic catalysts, where “metal and coordination atom interaction” cannot simulate the fine-tuning effect of organic ligands on metal catalytic centers in homogeneous catalysts. Therefore, certain chemical transformations in homogeneous catalysis cannot be perfectly replicated. Here, we used porous organic ligand polymers as the carrier, which effectively changes the charge regulation of nanoparticles and monoatomic metal catalysts. Drawing lessons from traditional homogeneous metal/ligand catalysis, we introduced various functional groups into the ligand polymers to adjust the electronic properties, and successfully realized the hydrosilylation of internal alkynes with high catalytic performance. The selectivity and catalytic efficiency under the Pd@POL-1 catalyst system were improved compared with previous studies. The internal alkynes with various structures can complete this reaction, and the ratio of E/Z can reach up to 100:1.