Solvent effect on mechanistic pathways in Rh-catalyzed hydroformylation of formaldehyde.

• Correlation of solvent descriptors with the hydroformylation activity established. • The net electron-giving ability of solvent is essential to the selectivity of glycolaldehyde. • Polar aprotic solvents influence the dissociation of Rh-H to form the anionic Rh species. • Generating MeOH is relatively easier in non-polar solvents. • HCHO activation requires a cooperation of anionic Rh species and protonated solvent molecule. The homogeneous catalytic hydroformylation of formaldehyde to glycolaldehyde is a key intermediate step for one-step synthesis of ethylene glycol from syngas. The effect of solvent nature on the catalytic response and mechanistic pathway has been rarely studied. A group of parameters (e.g., ε r , μ, α, β) describing the solvent electronic features were achieved for a descriptor database and correlated with the hydroformylation activity. The net electron donating ability has been found to govern the selectivity to glycolaldehyde. The DFT calculation demonstrates the stronger electron-donating solvents serve to lower the energy required for the dissociation of Rh-H to form the anionic rhodium species, which induces the anion mechanism that preferentially facilitates the glycolaldehyde generation. The polar aprotic solvents can be protonated in the dissociation of Rh-H to the anionic species and participate in the HCHO activation through the proton transfer from solvent molecules to HCHO, resulting in the formation of hydroxymethyl species. Graphic abstract [Display omitted]. [ABSTRACT FROM AUTHOR]