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

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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 ,

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

Keywords

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

UN SDGs

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

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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

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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.

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