The Nature of the Homonuclear Bond in Organic and Inorganic Dichalcogenides

The electronic structures of a number of disulfide R2S2, and peroxide, R2O2, compounds are theoretically investigated or reinvestigated, and the results are compared and contrasted with each other as well as with experimental data. The results show that the enormous bond length variations in these compounds cannot be explained on the basis of the simple electronegativity difference model, but rather one must take into consideration terminal group atomic orbital contributions to the predominately homonuclear bonding molecular orbitals. The qualitative aspects of the bonding parameters of a large number of disulfide and peroxide compounds are explained.