S=O homolytic bond dissociation enthalpies in sulfoxides

Abstract

The S=O bond dissociation enthalpies (BDE) were calculated using high-level ab initio methods including G3, G3B3, CBS-Q, CBS-4M, CCSD(T), and MP2. Based on the comparison of these theoretical values and experimental ones, the performances of a number of density functional theory (DFT) methods were then assessed. It was found that the B3P86 method gave the lowest root of mean square error. We therefore used this method to calculate the S=O BDEs of a number of substituted sulfoxides. The electronic effect of the substituents and the remote substituents effect of aryl-substituted sulfoxides on S=O BDE were investigated. In addition, a molecular orbital analysis of typical molecules was conducted in order to investigate the electronic effect on S=O BDEs. We also predicted several S=O BDE values of heteroaromatic substituted sulfoxides using the B3P86 method.