Abstract. The interaction of CT DNA by two anionic Ru(III) complexes with N-substituted salicylidenimine ligands was investigated by spectroscopic titration and cyclic voltammetry. The result gives a surprising evidence for intercalation of DNA by the negatively charged complex species containing non typical intercalating ligands with K b of order 10 4 M −1 . Na[RuCl 2 (N-R-5-X-salim) 2 ], where R represents butyl or phenyl and X = H, Cl, were characterized on the basis of elemental analysis, MALDI-TOF mass spectrometry, infrared, UV / visible spectroscopic measurements and cyclic voltammetry. (doi: 10.5562/cca2216)