Research on Silane-Free CO₂ Hydroformylation: Reaction Mechanisms with Ru₃(CO)₁₂ and Phosphine Catalysts

Coupling reverse water–gas shift (RWGS) with hydroformylation allows olefins to react with H₂/CO₂ to produce valuable aldehydes, which is a profitable reaction and helps with carbon fixation. However, temperature mismatch between the two reactions and limited mechanistic understanding hinder the rational design of catalysts.

Using density functional theory (DFT) calculations and experimental evaluations, we investigated the effects of different phosphine ligands and acid additives on the performance of silane-free CO₂ hydroformylation. Formic acid alters the CO₂ activation pathway and reduces the energy barrier, thereby improving catalytic activity and chemoselectivity. The effects of reaction conditions reveal a competitive relationship between CO₂ reduction and olefin carbonylation, suggesting that balancing RWGS and hydroformylation rates enhances catalytic performance.