Propylene hydroformylation catalyzed by rhodium-based catalysts with phosphine-sulfur ligands: a combined theoretical and experimental study.

Olefin hydroformylation is an important synthetic reaction that efficiently converts olefins into aldehydes. Rhodium-based catalysts are widely employed in industrial hydroformylation processes; however, enhancing their catalytic performance remains a significant challenge. In this study, we systematically investigate the impact of various sulfur-containing ligands on the catalytic performance of rhodium-based catalysts for olefin hydroformylation using density functional theory (DFT) calculations. Our findings reveal that sulfur-containing ligands form coordination bonds with rhodium, altering the geometric and electronic properties of the catalyst. These changes enhance the interactions between reaction intermediates and the catalyst, improving the stability of the key intermediate states and lowering the energy barriers of the rate-determining steps. Notably, catalysts with ligands featuring sulfur atoms linked to groups with higher electron affinity or bisulfur structures exhibit superior catalytic activity. Preliminary experimental validations further support the theoretical predictions, showing activity trends largely consistent with computational findings. This work elucidates the role of sulfur-containing ligands in rhodium-based catalysts for olefin hydroformylation and provides theoretical insights for designing more efficient catalysts for this reaction.