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.
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Hopkinson, A.C., Lien, M.H., Yates, K. et al. Quantum chemical studies on electrophilic addition. Theoret. Chim. Acta 44, 385–398 (1977). https://doi.org/10.1007/BF00547831
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DOI: https://doi.org/10.1007/BF00547831