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

doi:10.1002/jcc.26104

Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair S_N2 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 Journal › Article › Academic › peer-review

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Abstract

We have computationally studied the bimolecular nucleophilic substitution (S_N2) reactions of M_nNH₂ ⁽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 (S_N2-b) versus frontside attack (S_N2-f). The results were compared to the corresponding ion-pair S_N2 reactions involving F⁻ and OH⁻ nucleophiles. Our analyses with an extended activation strain model of chemical reactivity uncover and explain various trends in S_N2 reactivity along the nucleophiles F⁻, OH⁻, and (Formula presented.), including solvent and counterion effects.

Original language	English
Pages (from-to)	317-327
Number of pages	11
Journal	Journal of Computational Chemistry
Volume	41
Issue number	4
Early online date	11 Nov 2019
DOIs	https://doi.org/10.1002/jcc.26104
Publication status	Published - 5 Feb 2020

Funding

, 2005 . (e) This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number OCI‐1053575. N. C. Handy , A. J. Cohen , We acknowledge the funding provided by the Tertiary Education Commission (TEC) of Mauritius, the Netherlands Organization for Scientific Research (NWO), the Spanish Ministerio de Econom?a y Competitividad (CTQ2016-77558-R and MDM-2017-0767), and the Generalitat de Catalunya (2017SGR348). SEAGrid (http://www.seagrid.org) is acknowledged for computational resources and services for the selected results used in this publication.

Funders	Funder number
Extreme Science and Engineering Discovery Environment
Tertiary Education Commission
Generalitat de Catalunya	2017SGR348
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad	CTQ2016-77558-R, MDM-2017-0767
National Science Foundation	OCI‐1053575

UN SDGs

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

SDG 6 Clean Water and Sanitation

Keywords

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

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10.1002/jcc.26104

J Comput Chem - 2019 - Savoo - Activation Strain Analyses of Counterion and Solvent Effects on the Ion‐Pair SN2 Reaction ofFinal published version, 2.67 MBLicence: Article 25fa Dutch Copyright Act

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Cite this

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

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.",

keywords = "activation strain model, amide, DFT calculations, ion-pair S2, nucleophilic substitution, solvent effects",

author = "Nandini Savoo and Laloo, \{Jalal Z.A.\} and Lydia Rhyman and Ponnadurai Ramasami and Bickelhaupt, \{F. Matthias\} and Jordi Poater",

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AU - Savoo, Nandini

AU - Laloo, Jalal Z.A.

AU - Rhyman, Lydia

AU - Ramasami, Ponnadurai

AU - Bickelhaupt, F. Matthias

AU - Poater, Jordi

PY - 2020/2/5

Y1 - 2020/2/5

N2 - 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.

AB - 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.

KW - activation strain model

KW - amide

KW - DFT calculations

KW - ion-pair S2

KW - nucleophilic substitution

KW - solvent effects

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