Reaction of dichlorotris(triphenylphosphine) ruthenium(II) [RuCl2(PPh3)(3)] with 1,8-bis(2-pyridyl)-3,6-dithiaoctane (pdto), a (N2S2) tetradentate donor, yields a new compound [Ru(pdto)(PPh3)Cl]Cl (1), which has been fully characterized. H-1 and P-31 NMR studies of 1 in acetonitrile at several temperatures show the substitution of both coordinated chloride and triphenylphosphine with two molecules of acetonitrile, as confirmed by the isolation of the complex [Ru(pdto)(CH3CN)(2)]Cl-2 (2). Cyclic voltammetric and spectroelectrochernical techniques allowed us to determine the electrochemical behavior of compound 1. The substitution of the chloride and triphenylphosphine by acetonitrile molecules in the Ru(II) coordination sphere of compound 1 was also established by electrochemical studies. The easy substitution of this complex led us to use it as starting material to synthesize the substituted phenanthroline coordination compounds with (pdto) and ruthenium(II), [Ru(pdto)(4,7-diphenyl-1,10-phenanthroline)]Cl-2.4H(2)O (3), [Ru(pdto)(1,10-phenanthroline)]Cl-2.5H(2)O (4), [Ru(pdto)(5,6-dimethyl-1,10-phenanthroline)]Cl-2.5H(2)O (5), [Ru(pdto)(4,7-dimethyl-1,10-phenanthroline)]Cl-2.3H(2)O (6), and [Ru(pdto)(3,4,7,8-tetramethyl-1,10-phenanthroline)]Cl-2.4H(2)O (7). These compounds were fully characterized, and the crystal structure of 4 was obtained. Cyclic voltammetric and spectroelectrochemical techniques allowed us to determine their electrochemical behavior. The electrochemical oxidation processes in these compounds are related to the oxidation of ionic chlorides, and to the reversible transformation from Ru(II) to Ru(Ill). On the other hand, a single reduction process is associated to the reduction of the substituted phenanthroline in the coordination compound. The E-1/2 (phen/phen(-)) and E-1/2 (Ru-II/Ru-III) for the compounds (3-7) were evaluated, and, as expected, the modification of the substituted 1,10-phenanthrolines in the complexes also modifies the redox potentials. Correlations of both electrochemical potentials with pK(a) of the free 1,10-phenathrolines, lambda(max) MLCT transition band, and chemical shifts of phenanthrolines in these complexes were found, possibly as a consequence of the change in the electron density of the Ru(II) and the coordinated phenanthroline.