Non-empirical SCF-MO wave functions were computed for the two limiting structures of C2H3S+ with full geometry optimization using three different atomic orbital bases. It was found that the bridged structure (thiirenium ion) was somewhat more stable (1-14 kcal mol -1 depending on the basis set) than the open structure (β-thiovinyl cation). The barrier of interconversion between these two valence tautomers was calculated to be 12.8 kcal mol-1 without geometry optimization. The pyramidal inversion at sulphur in the thiirenium ion was computed to be 72.9 kcal mol-1.
|Number of pages||5|
|Journal||Journal of the Chemical Society, Perkin Transactions 2|
|Publication status||Published - Jan 1 1974|
ASJC Scopus subject areas