Revealing a double-inversion mechanism for the F−+CH3Cl SN2 reaction

István Szabó and Gábor Czakó ()
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István Szabó: Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University
Gábor Czakó: Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University

Nature Communications, 2015, vol. 6, issue 1, 1-6

Abstract: Abstract Stereo-specific reaction mechanisms play a fundamental role in chemistry. The back-side attack inversion and front-side attack retention pathways of the bimolecular nucleophilic substitution (SN2) reactions are the textbook examples for stereo-specific chemical processes. Here, we report an accurate global analytic potential energy surface (PES) for the F−+CH3Cl SN2 reaction, which describes both the back-side and front-side attack substitution pathways as well as the proton-abstraction channel. Moreover, reaction dynamics simulations on this surface reveal a novel double-inversion mechanism, in which an abstraction-induced inversion via a FH···CH2Cl− transition state is followed by a second inversion via the usual [F···CH3···Cl]− saddle point, thereby opening a lower energy reaction path for retention than the front-side attack. Quasi-classical trajectory computations for the F−+CH3Cl(ν1=0, 1) reactions show that the front-side attack is a fast direct, whereas the double inversion is a slow indirect process.

Date: 2015
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DOI: 10.1038/ncomms6972

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