Influence of the leaving group on the dynamics of a gas-phase SN2 reaction

Nature Chemistry
M SteiRoland Wester

Abstract

In addition to the nucleophile and solvent, the leaving group has a significant influence on SN2 nucleophilic substitution reactions. Its role is frequently discussed with respect to reactivity, but its influence on the reaction dynamics remains unclear. Here, we uncover the influence of the leaving group on the gas-phase dynamics of SN2 reactions in a combined approach of crossed-beam imaging and dynamics simulations. We have studied the reaction F(-) + CH3Cl and compared it to F(-) + CH3I. For the two leaving groups, Cl and I, we find very similar structures and energetics, but the dynamics show qualitatively different features. Simple scaling of the leaving group mass does not explain these differences. Instead, the relevant impact parameters for the reaction mechanisms are found to be crucial and the differences are attributed to the relative orientation of the approaching reactants. This effect occurs on short timescales and may also prevail in solution-phase conditions.

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Citations

Jan 23, 2016·The Journal of Physical Chemistry. a·Eduardo CarrascosaRoland Wester
May 5, 2016·The Journal of Physical Chemistry. a·Xu LiuRui Sun
Aug 10, 2016·The Journal of Physical Chemistry Letters·Yan WangMinghui Yang
Oct 27, 2016·The Journal of Chemical Physics·István Szabó, Gábor Czakó
Apr 11, 2017·The Journal of Physical Chemistry Letters·Xu LiuWilliam L Hase
Jun 10, 2017·The Journal of Physical Chemistry Letters·István SzabóGábor Czakó
Feb 20, 2018·Chemistry : a European Journal·Trevor A HamlinF Matthias Bickelhaupt
Mar 16, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Trevor A HamlinF Matthias Bickelhaupt
Jun 7, 2018·Chemical Communications : Chem Comm·Jia ChenJi-Chang Xiao
May 29, 2018·Chemistry : a European Journal·Boris GalabovWesley D Allen
Dec 12, 2018·Physical Chemistry Chemical Physics : PCCP·Golda Mensa-BonsuJan R R Verlet
Jan 9, 2019·Physical Chemistry Chemical Physics : PCCP·Balázs Olasz, Gábor Czakó
Jan 12, 2019·Physical Chemistry Chemical Physics : PCCP·Subha PratiharWilliam L Hase
Mar 29, 2019·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó
May 18, 2019·Chemical Communications : Chem Comm·Claire Vallance
Apr 2, 2016·Science·Jing Xie, William L Hase
Jul 21, 2017·Physical Chemistry Chemical Physics : PCCP·Yong-Tao MaWilliam L Hase
Aug 18, 2017·Physical Chemistry Chemical Physics : PCCP·Xu LiuRui Sun
Feb 6, 2020·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó
Apr 7, 2020·Physical Chemistry Chemical Physics : PCCP·Lulu LiDong H Zhang
Apr 23, 2020·Physical Chemistry Chemical Physics : PCCP·Tim MichaelsenRoland Wester
May 27, 2020·Physical Chemistry Chemical Physics : PCCP·Yan LiDunyou Wang
Jun 24, 2017·Nature Communications·Eduardo CarrascosaRoland Wester
Oct 12, 2018·The Journal of Chemical Physics·Kin Long Kelvin LeeMeredith J T Jordan
Jul 10, 2018·Science Advances·Martin SteiRoland Wester
May 4, 2017·Annual Review of Physical Chemistry·Jennifer Meyer, Roland Wester
Jul 10, 2017·The Journal of Chemical Physics·Tim MichaelsenRoland Wester
Nov 15, 2017·Chemical Society Reviews·Eduardo CarrascosaRoland Wester
Apr 10, 2018·Chemical Science·Eduardo CarrascosaRoland Wester
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Feb 16, 2021·Physical Chemistry Chemical Physics : PCCP·Xiaoyan JiJing Xie
Feb 26, 2021·The Journal of Physical Chemistry. a·Gábor CzakóDomonkos A Tasi
Jun 2, 2021·Mass Spectrometry Reviews·Roland Wester
Jun 17, 2021·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó

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