Theoretical and experimental comparison of the reactivity of the sulfanyl-closo-decaborate and sulfanyl-closo-dodecaborate anions and their mono-S-substituted derivatives

Abstract

In this work, we have extended the method proposed by Gabel for the preparation of mono- and di-S,S-substituted derivatives of sulfanyl-closo-dodecaborate anion [B12H11SH]2− to derivatives of the closo-decaborate anion. The method is based on the β-elimination of the propionitrile group of sulfonium derivatives [BnHn-1S(R)CH2CH2CN]− in the presence of bases with the formation of the corresponding mono-S-substituted derivatives and acrylonitrile. We also calculated the Fukui functions for the nucleophilic attack of the S-atom in the [B10H9SH]2− and [B12H11SH]2− anions and their mono-S-substituted derivatives using the Hirshfeld approach. As a result, the calculated value of nucleophilicity in the [B10H9SH]2− anion was found to be 5–10 times lower than in other compounds, which completely agrees with the experimental data.