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

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

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
DOIs	https://doi.org/10.1002/jcc.26104
Publication status	Published - 5 Feb 2020
Externally published	Yes

Keywords

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

ASJC Scopus subject areas

General Chemistry
Computational Mathematics

Access to Document

10.1002/jcc.26104

Cite this

@article{c440a0adbb7b43bbb31e747271082a83,

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 = "DFT calculations, activation strain model, amide, 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",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley Periodicals, Inc.",

year = "2020",

month = feb,

day = "5",

doi = "10.1002/jcc.26104",

language = "English",

volume = "41",

pages = "317--327",

journal = "Journal of Computational Chemistry",

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T1 - Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair SN2 Reaction of NH2− and CH3Cl

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 - DFT calculations

KW - activation strain model

KW - amide

KW - ion-pair S2

KW - nucleophilic substitution

KW - solvent effects

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U2 - 10.1002/jcc.26104

DO - 10.1002/jcc.26104

M3 - Article

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VL - 41

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JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

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