Quantum chemical studies on electrophilic addition - II. Reaction of chlorine with ethylene

Alan C. Hopkinson, Min H. Lien, Keith Yates, Imre G. Csizmadia

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Abstract

The geometries of the 2-chloroethyl and ethylenechloronium cations, two possible intermediates in the electrophilic addition of chlorine to ethylene, have been fully optimized using ab initio molecular orbital calculations employing the split valence shell 4-31G basis set. These geometries were then used to compute more accurate wave functions using Dunning's double-zeta basis set. The bridged chloronium ion was found to be more stable by 9.35 kcal/mole, the opposite order of stability from the C2H4F+ ions. Interconversion of the two C2H4Cl+ cations was computed to have a barrier of 6.25 kcal/mole. The activation energy for this chlorination reaction, using the ethylenechloronium cation and a chlorine anion at infinite separation as the model for the activated complex, was computed to be 128.7 kcal/mole, showing that this is not a feasible gas phase reaction.

Original languageEnglish
Pages (from-to)385-398
Number of pages14
JournalTheoretica chimica acta
Volume44
Issue number4
DOIs
Publication statusPublished - Dec 1 1977

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Keywords

  • 2-Chloroethyl and ethylenechloronium cations
  • Reaction profile for interconversion

ASJC Scopus subject areas

  • Chiropractics

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