J. Phys. Org. Chem., 5, 74-79 (1992).

DOI: 10.1002/poc.610050203

Comparative aromaticity study on heterocycles containing S, SO, and SO2

Owing to the importance of the concept of aromaticity, different indices have been developed to try to quantify this property. The possible π delocalization through an X[BOND]SOn[BOND]X group (X = C, N; n = 0, 1 or 2) could explain heteroaromaticity in rings containing the moiety. For that reason, the aromaticity of five-membered sulphurcontaining rings with different oxidation numbers (S, SO and SO2) and including no (thiophene), one (isothiazole) or two (1,2,5-thiadiazole) adjacent atoms was investigated. Ab initio calculations were carried out to determine geometrical parameters (planarity of the ring, bond length and bond order), electronic structure (charge distribution and dipolar moment) and the participation of d-orbitals of sulphur. According to these calculations, only compounds with S(II) can be considered to be aromatic, whereas compounds bearing S(IV) or S(VI) are better described as ylides.