How Solvation Influences the S_N2 versus E2 Competition.

ABSTRACT: We have quantum chemically investigated how solvation influences the competition between the S_N2 and E2 pathways of the model F^- + C₂H₅Cl reaction. The system is solvated in a stepwise manner by going from the gas phase, then via microsolvation of one to three explicit solvent molecules, then last to bulk solvation using relativistic density functional theory at (COSMO)-ZORA-OLYP/QZ4P. We explain how and why the mechanistic pathway of the system shifts from E2 in the gas phase to S_N2 upon strong solvation of the Lewis base (i.e., nucleophile/protophile). The E2 pathway is preferred under weak solvation of the system by dichloromethane, whereas a switch in reactivity from E2 to S_N2 is observed under strong solvation by water.

SUBMITTER: Hansen T 

PROVIDER: S-EPMC8822482 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature