Abstract: A theoretical investigation of solvent effects on hydroformylation has been carried out at the B3LYP/6-31G (d, p) level (LANL2DZ + Polar for Rh, P) via Onsager model. All stagnation points in the reaction potential profile are optimized completely under condition of cyclohexane (C6H12, ε=2.02), benzene (C6H6, ε=2.25), tetrahydrofuran (THF, ε=7.58), dichloromethane (CH2Cl2, ε=8.93), methanol (CH3OH, ε=32.63) and water (H2O, ε=78.39) as solvent respectively. The free energies and activating free energies are also calculated at the same level and comparison of the data in different solvents are made at all points. These results demonstrate that the activating free energies fall down with increasing of ε value of solvent. Therefore, water with ε=78.39 as solvent for hydroformylation of olefin is considered to be better than the others. The conclusion is consistent with a body of experimental studies.

Key words: Hydroformylation, Solvent effect, SCRF(self-consistent reaction field), Density functional theory(DFT)