Ligands L X of the type NS2 with S-aryl and S-alkyl substituents which incorporate the unit 2,6-bis(thiomethyl)pyridine are produced. Their reaction with [RuCl2(PPh3)3] and [RuCl2(DMSO)4] produces the first reported Ru(II)/NS2 complexes. They present the general formulas [RuCl2(L X )L‘], where L‘ = PPh3 or DMSO. Several isomers are possible; however, only two have been found in each reaction. The 1H NMR spectra show that the HaHb proton atoms of the pyridine−CHaHb−thioether unit are nonisochronous. A Δδ(HaHb) value close to 1 ppm is observed for the cis complexes while this is smaller for the trans analogues. The possible distinct isomers are discussed in terms of steric effects. It is hypothesized that the trans -dl, the trans -meso, and the cis -meso-E would be the structures more favored. Those structures have been confirmed by X-ray diffraction analysis of trans -dl-[RuCl2(L1)(DMSO)]·0.5MeOH, cis-[RuCl2(L5)(PPh3)]·CH2Cl2, and trans -meso-[RuCl2(L6)(PPh3)]·1.5MeOH.

Ligands LX of the type NS(2) with S-aryl substituents which incorporate the unit 2,6-bis(thiomethyl)pyridine modified with functional groups bonded to the aromatic moieties, either on the phenyl or on the pyridine, are produced. Electron-withdrawing groups, 3-chloro and 4-nitro, that reduce the pyridine basicity have been introduced. Methoxy or methoxycarbonyl substituents have been incorporated on the thiophenyl moieties. The comparative results from the reaction of these ligands with Cu(ClO(4))(2).6H(2)O and [RuCl(2)(PPh(3))(3)] have revealed that their coordination capacity has not been greatly modified as a result of the introduced groups. Complexes of general formulas [Cu(LX)][ClO(4)](2), except for L5, and [RuCl(2)(LX)(PPh(3))], have been obtained, respectively. The electronic characteristics of these complexes have been studied by cyclic voltammetry experiments. The structures of 2,6-bis[(2'-methoxycarbonyl)phenylthio-methyl]-4-nitropyridine (L5) and [RuCl(2)(L5)(PPh(3))].2CCl(4) have been characterized by single-crystal X-ray diffraction methods.