Ion-Pair SN2 Reaction of OH− and CH3Cl: Activation Strain Analyses of Counterion and Solvent Effects

Jalal Z.A. Laloo; Lydia Rhyman; Olatz Larrañaga; Ponnadurai Ramasami; F. Matthias Bickelhaupt; Abel de Cózar

doi:10.1002/asia.201800082

Ion-Pair S_N2 Reaction of OH⁻ and CH₃Cl: Activation Strain Analyses of Counterion and Solvent Effects

Jalal Z.A. Laloo, Lydia Rhyman, Olatz Larrañaga, Ponnadurai Ramasami^*, F. Matthias Bickelhaupt, Abel de Cózar

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

We have theoretically studied the non-identity S_N2 reactions of M_nOH⁽ⁿ⁻¹⁾+CH₃Cl (M⁺=Li⁺, Na⁺, K⁺, and MgCl⁺; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M⁺ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (S_N2-b) and frontside (S_N2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.

Original language	English
Pages (from-to)	1138-1147
Number of pages	10
Journal	Chemistry - An Asian Journal
Volume	13
Issue number	9
DOIs	https://doi.org/10.1002/asia.201800082
Publication status	Published - 4 May 2018

Keywords

activation strain model
density functional calculations
ion pairs
nucleophilic substitution
solvent effects

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@article{b0bebf2b24b94bac922322cff9ce3438,

title = "Ion-Pair SN2 Reaction of OH− and CH3Cl: Activation Strain Analyses of Counterion and Solvent Effects",

abstract = "We have theoretically studied the non-identity SN2 reactions of MnOH(n−1)+CH3Cl (M+=Li+, Na+, K+, and MgCl+; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M+ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (SN2-b) and frontside (SN2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.",

keywords = "activation strain model, density functional calculations, ion pairs, nucleophilic substitution, solvent effects",

author = "Laloo, {Jalal Z.A.} and Lydia Rhyman and Olatz Larra{\~n}aga and Ponnadurai Ramasami and Bickelhaupt, {F. Matthias} and {de C{\'o}zar}, Abel",

year = "2018",

month = may,

day = "4",

doi = "10.1002/asia.201800082",

language = "English",

volume = "13",

pages = "1138--1147",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "John Wiley and Sons Ltd",

number = "9",

}

TY - JOUR

T1 - Ion-Pair SN2 Reaction of OH− and CH3Cl

T2 - Activation Strain Analyses of Counterion and Solvent Effects

AU - Laloo, Jalal Z.A.

AU - Rhyman, Lydia

AU - Larrañaga, Olatz

AU - Ramasami, Ponnadurai

AU - Bickelhaupt, F. Matthias

AU - de Cózar, Abel

PY - 2018/5/4

Y1 - 2018/5/4

N2 - We have theoretically studied the non-identity SN2 reactions of MnOH(n−1)+CH3Cl (M+=Li+, Na+, K+, and MgCl+; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M+ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (SN2-b) and frontside (SN2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.

AB - We have theoretically studied the non-identity SN2 reactions of MnOH(n−1)+CH3Cl (M+=Li+, Na+, K+, and MgCl+; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M+ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (SN2-b) and frontside (SN2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.

KW - activation strain model

KW - density functional calculations

KW - ion pairs

KW - nucleophilic substitution

KW - solvent effects

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DO - 10.1002/asia.201800082

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JF - Chemistry - An Asian Journal

SN - 1861-4728

IS - 9

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