Solvent-induced dual nucleophiles and the α-effect in the S_N2 versus E2 competition.

ABSTRACT: We have quantum chemically investigated how microsolvation affects the various E2 and S_N2 pathways, their mutual competition, and the α-effect of the model reaction system HOO^-(H₂O)_n + CH₃CH₂Cl, at the CCSD(T) level. Interestingly, we identify the dual nature of the α-nucleophile HOO^- which, upon solvation, is in equilibrium with HO^-. This solvent-induced dual appearance gives rise to a rich network of competing reaction channels. Among both nucleophiles, S_N2 is always favored over E2, and this preference increases upon increasing microsolvation. Furthermore, we found a pronounced α-effect, not only for S_N2 substitution but also for E2 elimination, i.e., HOO^-

SUBMITTER: Wu X 

PROVIDER: S-EPMC11022550 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature