S_N2 versus E2 Competition of F^- and PH₂^- Revisited.

ABSTRACT: We have quantum chemically analyzed the competition between the bimolecular nucleophilic substitution (S_N2) and base-induced elimination (E2) pathways for F^- + CH₃CH₂Cl and PH₂^- + CH₃CH₂Cl using the activation strain model and Kohn-Sham molecular orbital theory at ZORA-OLYP/QZ4P. Herein, we correct an earlier study that intuitively attributed the mechanistic preferences of F^- and PH₂^-, i.e., E2 and S_N2, respectively, to a supposedly unfavorable shift in the polarity of the abstracted β-proton along the PH₂^--induced E2 pathway while claiming that ″...no correlation between the thermodynamic basicity and E2 rate should be expected.″

SUBMITTER: Vermeeren P 

PROVIDER: S-EPMC7656514 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature