Nucleophilic Substitution (SN 2): Dependence on Nucleophile, Leaving Group, Central Atom, Substituents, and Solvent

Trevor A. Hamlin; Marcel Swart; F. Matthias Bickelhaupt

doi:10.1002/cphc.201701363

Nucleophilic Substitution (SN 2): Dependence on Nucleophile, Leaving Group, Central Atom, Substituents, and Solvent

Trevor A. Hamlin, Marcel Swart^*, F. Matthias Bickelhaupt

^*Corresponding author for this work

Research output: Contribution to Journal › Review article › Academic › peer-review

Abstract

The reaction potential energy surface (PES), and thus the mechanism of bimolecular nucleophilic substitution (S_N2), depends profoundly on the nature of the nucleophile and leaving group, but also on the central, electrophilic atom, its substituents, as well as on the medium in which the reaction takes place. Here, we provide an overview of recent studies and demonstrate how changes in any one of the aforementioned factors affect the S_N2 mechanism. One of the most striking effects is the transition from a double-well to a single-well PES when the central atom is changed from a second-period (e. g. carbon) to a higher-period element (e.g, silicon, germanium). Variations in nucleophilicity, leaving group ability, and bulky substituents around a second-row element central atom can then be exploited to change the single-well PES back into a double-well. Reversely, these variations can also be used to produce a single-well PES for second-period elements, for example, a stable pentavalent carbon species.

Original language	English
Pages (from-to)	1315-1330
Number of pages	16
Journal	ChemPhysChem
Volume	19
Issue number	11
Early online date	15 Mar 2018
DOIs	https://doi.org/10.1002/cphc.201701363
Publication status	Published - 5 Jun 2018

Funding

The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovación (MICINN, project number CTQ2008-06532/BQU), the DIUE of the Generalitat de Catalunya (project number 2009SGR528), the Netherlands Organization for Scientific Research (NWO), the Planetary and Exo-Planetary Science program (PEPSci), and the Dutch Astrochemistry Network (DAN). The authors thank Stephanie van der Lubbe, Dr. Jörn Nitsch, Pascal Vermeeren, Dr. Lando P. Wolters, and the reviewers for helpful discussions and constructive criticism of the manuscript.

Funders	Funder number
Dutch Astrochemistry Network
Netherlands Organization for Scientific Research
Planetary and Exo-Planetary Science program
Generalitat de Catalunya	2009SGR528
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Ciencia e Innovación	CTQ2008-06532/BQU

Keywords

bimolecular nucleophilic substitutions (S2)
hypervalency
organic chemistry
potential energy surface
reaction barriers

UN SDGs

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

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abstract = "The reaction potential energy surface (PES), and thus the mechanism of bimolecular nucleophilic substitution (SN2), depends profoundly on the nature of the nucleophile and leaving group, but also on the central, electrophilic atom, its substituents, as well as on the medium in which the reaction takes place. Here, we provide an overview of recent studies and demonstrate how changes in any one of the aforementioned factors affect the SN2 mechanism. One of the most striking effects is the transition from a double-well to a single-well PES when the central atom is changed from a second-period (e. g. carbon) to a higher-period element (e.g, silicon, germanium). Variations in nucleophilicity, leaving group ability, and bulky substituents around a second-row element central atom can then be exploited to change the single-well PES back into a double-well. Reversely, these variations can also be used to produce a single-well PES for second-period elements, for example, a stable pentavalent carbon species.",

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N2 - The reaction potential energy surface (PES), and thus the mechanism of bimolecular nucleophilic substitution (SN2), depends profoundly on the nature of the nucleophile and leaving group, but also on the central, electrophilic atom, its substituents, as well as on the medium in which the reaction takes place. Here, we provide an overview of recent studies and demonstrate how changes in any one of the aforementioned factors affect the SN2 mechanism. One of the most striking effects is the transition from a double-well to a single-well PES when the central atom is changed from a second-period (e. g. carbon) to a higher-period element (e.g, silicon, germanium). Variations in nucleophilicity, leaving group ability, and bulky substituents around a second-row element central atom can then be exploited to change the single-well PES back into a double-well. Reversely, these variations can also be used to produce a single-well PES for second-period elements, for example, a stable pentavalent carbon species.

AB - The reaction potential energy surface (PES), and thus the mechanism of bimolecular nucleophilic substitution (SN2), depends profoundly on the nature of the nucleophile and leaving group, but also on the central, electrophilic atom, its substituents, as well as on the medium in which the reaction takes place. Here, we provide an overview of recent studies and demonstrate how changes in any one of the aforementioned factors affect the SN2 mechanism. One of the most striking effects is the transition from a double-well to a single-well PES when the central atom is changed from a second-period (e. g. carbon) to a higher-period element (e.g, silicon, germanium). Variations in nucleophilicity, leaving group ability, and bulky substituents around a second-row element central atom can then be exploited to change the single-well PES back into a double-well. Reversely, these variations can also be used to produce a single-well PES for second-period elements, for example, a stable pentavalent carbon species.

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KW - reaction barriers

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Nucleophilic Substitution (SN 2): Dependence on Nucleophile, Leaving Group, Central Atom, Substituents, and Solvent

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