Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair SN2 Reaction of NH2− and CH3Cl

Nandini Savoo, Jalal Z.A. Laloo, Lydia Rhyman, Ponnadurai Ramasami, F. Matthias Bickelhaupt, Jordi Poater*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We have computationally studied the bimolecular nucleophilic substitution (SN2) reactions of MnNH2 (n−1) + CH3Cl (M+ = Li+, Na+, K+, and MgCl+; n = 0, 1) in the gas phase and in tetrahydrofuran solution at OLYP/6-31++G(d,p) using polarizable continuum model implicit solvation. We wish to explore and understand the effect of the metal counterion M+ and of solvation on the reaction profile and the stereochemical preference, that is, backside (SN2-b) versus frontside attack (SN2-f). The results were compared to the corresponding ion-pair SN2 reactions involving F and OH nucleophiles. Our analyses with an extended activation strain model of chemical reactivity uncover and explain various trends in SN2 reactivity along the nucleophiles F, OH, and (Formula presented.), including solvent and counterion effects.

Original languageEnglish
Pages (from-to)317-327
Number of pages11
JournalJournal of Computational Chemistry
Volume41
Issue number4
Early online date11 Nov 2019
DOIs
Publication statusPublished - 5 Feb 2020

Keywords

  • activation strain model
  • amide
  • DFT calculations
  • ion-pair S2
  • nucleophilic substitution
  • solvent effects

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