Abstract
Valence-bond (VB) correlation diagrams are used for the analysis of sulfur hypervalent compounds. It is shown that the stability of (10-S-4) sulfuranes is closely related to the electronegativity of the apical substituents. Moreover, it is predicted that an antisymmetrical bond stretch of apical bonds is easier with less-electronegative substituents. The electronic structure of (9-S-3) sulfuranyl radicals is analyzed by means of ab initio calculations. VB correlation diagrams are then used to discuss the factors which favor the σ or π nature of these radicals. Qualitative arguments are developed for predicting the possible metastability of these radicals.
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