Synthesis and characterization of dithioethers, and their RuII and RuIII complexes

The syntheses of nine, new dithioethers of the type RS(CH2)xSR, where x = 2 or 3 and R is an alkyl chain, as well as the known x = 2, R = phenyl or cyclohexyl compounds, are reported. The known dithioethers react with RuCl3·3H2O to form trans-RuCl2(dithioether)2 complexes 1 (R = Ph) and 2 (R = C6H11), whereas from the other dithioethers RuCl2[RS(CH2)xSR]2(μ-Cl)2 complexes have been isolated, where x = 3, and R = Et (complex 3), nPr (complex 4), nBu (complex 5), and R = npentyl (complex 6). The complexes are well characterized, including X-ray structures for complexes 1–4. The interest in these compounds stems from oxidation of the dithioethers to the corresponding disulfoxides and their Ru complexes.