Reaction mechanism conversion induced by the contest of nucleophile and leaving group

Abstract

Direct dynamic simulations have been employed to investigate the OH⁻ + CH₃Cl reaction with the chosen B3LYP/aug-cc-pVDZ method. The calculated rate coefficient for the bimolecular nucleophilic substitution reaction (S_N2), 1.0 × 10⁻⁹ cm³ mol⁻¹ s⁻¹ at 300 K, agrees well with the experimental result of (1.3–1.6) × 10⁻⁹ cm³ mol⁻¹ s⁻¹. The simulations reveal that the majority of the S_N2 reactions are temporarily trapped in the hydrogen-bonded complex at E_coll = 0.89 kcal mol⁻¹. Importantly, the influences of the leaving group and nucleophile have been discussed by comparisons of X⁻ + CH₃Y (X = F, OH; Y = Cl, I) reactions. For the X = F⁻ reactions, the reaction probability of S_N2 increases along the increased leaving group ability Cl < I, suggesting that the thermodynamic factor plays a key role. The indirect mechanisms were found to be dominant for both reactions. In contrast, for X = OH⁻, the fraction of S_N2 drops with the enhanced leaving group ability. In particular, a dramatic transition occurs for the dominant atomic reaction mechanisms, i.e., from complex-mediated indirect to direct, implying an interesting contest between the leaving group and the nucleophile and the importance of the dynamic factors, i.e., the dipole moment, steric hindrance, and electronegativity.