Constructing an electron-deficient Ru-based catalyst for heterogeneous hydrocarboxylation of olefins

The hydrocarboxylation of olefins represents a classical and atom-economical route for the synthesis of organic carboxylic acids. However, conventional catalytic systems generally suffer from severe corrosivity, poor catalyst stability, and difficulties in recovering active metal species, which significantly hinder the industrial application of olefin hydrocarboxylation. In this work, a novel porous organic polymer support, NPh 3 -SO 3 H-POPs, was synthesized via free-radical polymerization, followed by the preparation of a heterogeneous Ru 1 /NPh 3 -SO 3 H-POPs catalyst through metalation of RuCl 3 as a precursor. In the hydrocarboxylation of ethylene, the catalyst achieved an ethylene conversion of nearly 60.0% with a propionic acid selectivity of 99.9%, while maintaining stable catalytic performance over five consecutive reactions. Comprehensive characterization studies combined with density functional theory (DFT) calculations revealed that the -NPh 3 functional groups coordinated with ruthenium species through an appropriate coordination strength, which plays a crucial role in governing catalytic activity. This work offers new insights into the rational design of highly efficient heterogeneous Ru-based catalysts through precise modulation of metal-ligand coordination interactions.