Ion-Pair SN2 Substitution: Activation Strain Analyses of Counter-Ion and Solvent Effects

I.Z.A. Laloo, L. Rhyman, P. Ramasami, F.M. Bickelhaupt, A. de Cozar

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The ion-pair SN2 reactions of model systems MnFn−1+CH3Cl (M+=Li+, Na+, K+, and MgCl+; n=0, 1) have been quantum chemically explored by using DFT at the OLYP/6-31++G(d,p) level. The purpose of this study is threefold: 1) to elucidate how the counterion M+ modifies ion-pair SN2 reactivity relative to the parent reaction F−+CH3Cl; 2) to determine how this influences stereochemical competition between the backside and frontside attacks; and 3) to examine the effect of solvation on these ion-pair SN2 pathways. Trends in reactivity are analyzed and explained by using the activation strain model (ASM) of chemical reactivity. The ASM has been extended to treat reactivity in solution. These findings contribute to a more rational design of tailor-made substitution reactions.
Original languageEnglish
Pages (from-to)4431-4439
Number of pages9
JournalChemistry: A European Journal
Volume22
Issue number13
DOIs
Publication statusPublished - 2016

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