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

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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
Early online date	13 Feb 2018
DOIs	https://doi.org/10.1002/asia.201800082
Publication status	Published - 4 May 2018

Funding

The authors acknowledge facilities from Vrije University of Amsterdam, University of the Basque Country (UPV/EHU), and University of Mauritius. O. L. gratefully acknowledges the UPV/EHU for her postdoctoral grant. This work was supported by funding provided by the Mauritius Tertiary Education Commission (TEC), the Spanish Ministry of Economy and Competitiveness (MINECO CTQ2013-45415P and CTQ2016-80375P), and the Netherlands Organization for Scientific Research (NWO-CW and NWO-EW). We also thank SURFsara (www.surfsara.nl) for the support in using the Lisa Computer Cluster, and Gridchem and SGI-IZO-SGIker (UPV/EHU) for generous allocation of computational resources.

Funders	Funder number
NWO-CW
NWO-EW
Netherlands Organization for Scientific Research
Spanish Ministry of Economy and Competitiveness
Tertiary Education Commission
Ministerio de Economía y Competitividad	CTQ2013-45415P, CTQ2016-80375P
Euskal Herriko Unibertsitatea
University of Mauritius

Keywords

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

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/asia.201800082

Ion-Pair SN2 Reaction of OH− and CH3Cl Activation Strain Analyses of Counterion and Solvent EffectsFinal published version, 2.04 MBLicence: Article 25fa Dutch Copyright Act

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Cite this

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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.",

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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",

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AU - Laloo, Jalal Z.A.

AU - Rhyman, Lydia

AU - Larrañaga, Olatz

AU - Ramasami, Ponnadurai

AU - Bickelhaupt, F. Matthias

AU - de Cózar, Abel

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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.

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KW - density functional calculations

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KW - solvent effects

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