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

Martin Stei, Eduardo Carrascosa, Martin A. Kainz, Aditya H. Kelkar, Jennifer Meyer, István Szabó, G. Czakó, Roland Wester

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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.

Original languageEnglish
Pages (from-to)151-156
Number of pages6
JournalNature Chemistry
Volume8
Issue number2
DOIs
Publication statusPublished - Feb 1 2016

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Gases
Nucleophiles
Substitution reactions
Imaging techniques
Computer simulation

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Stei, M., Carrascosa, E., Kainz, M. A., Kelkar, A. H., Meyer, J., Szabó, I., ... Wester, R. (2016). Influence of the leaving group on the dynamics of a gas-phase SN2 reaction. Nature Chemistry, 8(2), 151-156. https://doi.org/10.1038/nchem.2400

Influence of the leaving group on the dynamics of a gas-phase SN2 reaction. / Stei, Martin; Carrascosa, Eduardo; Kainz, Martin A.; Kelkar, Aditya H.; Meyer, Jennifer; Szabó, István; Czakó, G.; Wester, Roland.

In: Nature Chemistry, Vol. 8, No. 2, 01.02.2016, p. 151-156.

Research output: Contribution to journalArticle

Stei, M, Carrascosa, E, Kainz, MA, Kelkar, AH, Meyer, J, Szabó, I, Czakó, G & Wester, R 2016, 'Influence of the leaving group on the dynamics of a gas-phase SN2 reaction', Nature Chemistry, vol. 8, no. 2, pp. 151-156. https://doi.org/10.1038/nchem.2400
Stei M, Carrascosa E, Kainz MA, Kelkar AH, Meyer J, Szabó I et al. Influence of the leaving group on the dynamics of a gas-phase SN2 reaction. Nature Chemistry. 2016 Feb 1;8(2):151-156. https://doi.org/10.1038/nchem.2400
Stei, Martin ; Carrascosa, Eduardo ; Kainz, Martin A. ; Kelkar, Aditya H. ; Meyer, Jennifer ; Szabó, István ; Czakó, G. ; Wester, Roland. / Influence of the leaving group on the dynamics of a gas-phase SN2 reaction. In: Nature Chemistry. 2016 ; Vol. 8, No. 2. pp. 151-156.
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