Ab initio SCF-MO study of the reaction intermediates formed by addition of thiohypochlorous acid to ethylene
Abstract
Non-empirical SCF-MO calculations, using two different basis sets, were carried out on a cyclic sulphurane and a thiiranium–chloride ion-pair. The calculated energies indicated that in the gas phase the covalent cyclic sulphurane is favoured over the ionic species. The activation energy for the internal collapse of the cyclic sulphurane to product was calculated to be 42 kcal mol–1, well below the energy of the thiiranium–chloride ion-pair. These results support the suggestion that thiiranium ions prevail in polar solvents but tetracovalent sulphur intermediates are favoured in solvents of low polarity.
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