Competitive dynamics of E2 and SN2 reaction driven by collision energy and leaving group.

Abstract

The competition between E2 and SN2 reactions is essential in organic chemistry. In this paper, the reaction mechanism of F- + CH3CH2Cl is investigated utilizing direct dynamics simulations, and unravel how the collision energy (Ecoll) and the leaving group affect the competition between SN2 and E2 in the F- + CH3CH2Y (Y = Cl and Br) reactions. Simulation results for F- + CH3CH2Cl reaction show that the anti-E2 channel is dominant, but with the increase of Ecoll from 0.04 to 1.9 eV the branching ratio of the anti-E2 pathway significantly decreases by 21%, and the SN2 pathway becomes more important. A transition from indirect to direct reaction has been revealed when Ecoll is increased from 0.04 to 1.90 eV. At lower Ecoll, a large ratio of indirect events occurs via a long-lived hydrogen-bonded complex, and as the collision energy is increased, the lifetimes of the hydrogen-bonded complexes are shortened, due to an initial faster relative velocity. The simulation results of F- + CH3CH2Cl are further compared with the F- + CH3CH2Br reaction at Ecoll of 0.04 eV. Changing the leaving group from Cl to Br drastically suppresses the indirect events of anti-E2 with a branching ratio decreasing from 0.46 to 0.36 due to the mass effect, and promotes direct rebound mechanism resulting from a looser transition state geometry caused by varied electronegativity.