Journal of Physical Chemistry A, Vol.121, No.5, 1078-1085, 2017
Competing E2 and S(N)2 Mechanisms for the F- + CH3CH2I Reaction
Anti-E2,syn-E2, inv-, and ret-SN2 reaction channels for the gas-phase reaction of F- + CH3CH2I were characterized with a variety of 20 electronic structure calculations. Geometrical analysis confirmed synchronous E2-type transition states for the elimination of the current reaction, instead of nonconcerted processes through El cb-like and El-like mechanisms. Importantly, the controversy concerning the reactant complex for anti-E2 and inv-S-N(2) paths has been clarified in the present work. A positive barrier of +19.2 kcal/mol for ret-SN2 shows the least feasibility to occur at room r" RC temperature. Negative activation energies (-16.9, -16.0, and 4.9 kcal/mol, respectively) for inv-SN2, anti-E2, and syn-E2 indicate that inv-SN2 and anti E2 mechanisms significantly prevail over the eclipsed elimination. Varying the leaving group for a series of reactions F- + CH3CH2Y (Y = F, Cl, Br, and I) leads to monotonically decreasing barriers, which relates to the gradually looser TS structures following the order F > Cl > Br > I. The reactivity of each channel nearly holds unchanged except :for the perturbation between anti-E2 and inv-SN2. RRKM calculation reveals that the reaction of the fluorine ion with ethyl iodide occurs predominately via anti-E2 elimination, and the inv-SN2 pathway is suppressed, although it is energetically favored. This phenomenon indicates that, in evaluating the competition between E2 and SN2 processes, the kinetic or dynamical factors may play a significant role. By comparison with benchmark CCSD(T) energies, MP2, CAM-B3LYP, and M06 methods are recommended to perform dynamics simulations of the title reaction.