d/ ppm 3.5 2.2 1.6 pH N O OH N O OH Abstract Complex formation processes of rhodium(III)-η 5 -pentamethylcyclopentadienyl cation [RhCp*(H 2 O) 3 ] 2+ with 1,2-dimethyl-3-hydroxy-pyridin-4(1H)-one (deferiprone, dhp) and pyridine-2-carboxylic acid (pic) were studied with the aid of pH-potentiometry, 1 H NMR and UV-visible spectrophotometry in aqueous solution in the presence and in the absence of chloride ions. Stoichiometry and overall stability constants of the complexes formed were determined. Formation of mononuclear, mono-ligand complexes such as [RhCp*(L)Z] (where L = dhp or pic; Z = Clor H 2 O) and mixed-hydroxido species [RhCp*(L)(OH)] was found. Relatively high pK a values (9.32-11.90) were determined for the hydrolysis of the [RhCp*(L)Z] complexes. [RhCp*(L)Z] species predominate at physiological pH, and negligible decomposition is probable only at low micromolar concentrations. More favored complex formation was found in the case of pic. Stability of the studied organorhodium complexes was compared to analogous Ru(II)(h 6 -p-cymene) compounds. In addition, the aqua/chlorido ligand replacement reaction in the complexes [RhCp*(L)(H 2 O)] + of dhp and pic was monitored to provide equilibrium constants with which the extent of aquation at various chloride concentrations can be estimated. Single crystals of [RhCp*(dhp)Cl] suitable for Xray diffraction analysis were also obtained. The [RhCp*(L)Cl] complexes of dhp and pic were tested for cytotoxicity in various human cancer cell lines where they showed activity depending on the attached ligand scaffold.