Several ruthenium(II)-chloro-dimethylsulfoxide complexes with formulae [RuCl2(DMSO)(k3-L1)] or [RuCl(DMSO)(k4-L2)]+, where L1 = [9]aneS3 (2) or ttbt (5) and L2 = [12]aneS4 (3), [14]aneS4 (4) or [14]aneN4 (6), have been synthesized from cis,fac-[RuCl2(S-DMSO)3(O-DMSO)] (1) and the respective macrocycle. They were spectroscopically characterized by FT-IR, FT-Raman, NMR, and UV/Vis. Particular attention was given to fac-[RuCl2(DMSO)(k3-ttbt)] (5), the first octahedral complex of ttbt, which was also studied by DFT calculations. The behavior of the complexes in coordinating solvents water, acetonitrile, and dimethylsulfoxide was studied to understand their reactivity and predict the resulting ions formed in solution. The role of the counter ion (Cl- vs. PF6- ) was also evaluated. The results indicate that the chosen macrocycle, the counter-ion, and the solvent have a direct impact on the chemical species formed in solution.