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Issue 15, 2021
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Facilitated inversion complicates the stereodynamics of an SN2 reaction at nitrogen center

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Abstract

Bimolecular nucleophilic substitution (SN2) reactions at carbon center are well known to proceed with the stereospecific Walden-inversion mechanism. Reaction dynamics simulations on a newly developed high-level ab initio analytical potential energy surface for the F + NH2Cl nitrogen-centered SN2 and proton-transfer reactions reveal a hydrogen-bond-formation-induced multiple-inversion mechanism undermining the stereospecificity of the N-centered SN2 channel. Unlike the analogous F + CH3Cl SN2 reaction, F + NH2Cl → Cl + NH2F is indirect, producing a significant amount of NH2F with retention, as well as inverted NH2Cl during the timescale within the unperturbed NH2Cl molecule gets inverted with only low probability, showing the important role of facilitated inversions via an FH…NHCl-like transition state. Proton transfer leading to HF + NHCl is more direct and becomes the dominant product channel at higher collision energies.

Graphical abstract: Facilitated inversion complicates the stereodynamics of an SN2 reaction at nitrogen center

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Supplementary files

Article information


Submitted
26 Jan 2021
Accepted
12 Mar 2021
First published
24 Mar 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 5410-5418
Article type
Edge Article

Facilitated inversion complicates the stereodynamics of an SN2 reaction at nitrogen center

D. Papp and G. Czakó, Chem. Sci., 2021, 12, 5410
DOI: 10.1039/D1SC00490E

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