Stereoelectronic Effects: A Powerful Concept in Explaining Kinetic and Thermodynamic Aspects of Retro Cheletropic Reactions

Abstract

Kinetic and thermodynamic aspects of the retro cheletropic reaction of sulfur dioxide extrusion have been investigated. The interaction of the X–S bond (X=NH, S, O and CH2) and oxygen lone pairs of SO2 showed remarkable stereoelectronic effects and its correlation with the difference between computed and empirical bond length (Δl) have been analysed. The facility of the reaction in the case of four derivatives (X=NH, S, O and CH2) has been investigated from the viewpoint of product delocalisation energy. In addition, substitution effects have been studied on the relative Gibbs free energy of reaction for the oxygen derivative (X=O). Moreover, a correlation has been found between the Gibbs free energy of reaction in the presence of the substituent and Δl as a criterion for the value of the interaction between the X–S bond and oxygen lone pairs of the SO2 group. Finally, a new method based on electron density has been used for evaluation of the synchronicity values of the reaction. According to the corresponding diagrams, the calculated synchronicity values of the Wiberg bond indices and electron density are in good agreement.