Interaction between functional groups and its consequences in oxidation of thioethers

Factors which affect the oxidation and ionization potentials of thioethers and the lifetimes of sulfur cation radicals have been investigated. Neighboring sulfur participation lowers the oxidation potential of thioethers and neighboring oxygen stabilizes sulfur cation radicals by S-O bond formation. The oxidation and ionization potentials of 1,3-dithiane are reduced by 2-stannyl groups due to interaction of the C-Sn bond with the sulfur 3p lone pair orbitals. Annulation of a naphthalene ring to 1,5-dithiocane increases lone pair-lone pair interaction lowering its ionization potential but not its oxidation potential.