Abstract
The structure of (ethylthio)bullvalene has been determined in solution and solid state. Whereas the structure of the title compound in the crystal is 4-(ethylthio)tricyclo[3.3.2.0]deca-3,6,9-triene, in solution a mixture of the 4-(ethylthio)-(15%) and 3-(ethylthio)-bullvalene (85%) has been detected. The dynamics of the valence tautomerism has been studied by variable temperature 1H n.m.r. spectroscopy. A comparison between the experimentally determined thermodynamic and kinetic quantitites of the valence tautomerism with MINDO/3, MNDO, and force-field calculations shows very good agreement between theory and experiment.

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