Influence of the Leaving Group on the Dynamics of a Gas Phase SN2 Reaction

Abstract: In addition to nucleophile and solvent, the leaving group has a significant influence on nucleophilic substitution (SN2) reactions. Its role is frequently discussed with respect to reactivity, but its influence on the reaction dynamics remains obscured. Here, we uncover the influence of the leaving group on the gas phase dynamics of SN2 reactions in a combined approach of crossed-beam imaging and dynamics simulations. We have studied the reaction F- + CH3Cl and compared it to F- + CH3I. For the two leaving groups Cl and I we find very similar structures and energetics, but the dynamics show qualitatively different features. Simple scaling of the leaving group mass does not explain these differences. Instead, the relevant impact parameters for the reaction mechanisms are found to be crucial, which is attributed to the relative orientation of the approaching reactants. This effect occurs on short time scales and may also prevail under solution phase conditions.