New stable cationic organogold(III) complexes containing the 'pincer' iminophosphorane ligand (2-C 6 H 4 -PPh 2 =NPh) have been prepared by reaction of the previously described [Au{κ 2 -C,N-C 6 H 4 (PPh 2 =N(C 6 H 5 )-2}Cl 2 ] 1 and a combination of sodium or silver salts and appropriate ligands. The presence of the P atom in the PR 3 fragment has been used as a "spectroscopic marker" to study the in vitro stability (and oxidation state) of the new organogold complexes in solvents like DMSO and water. Compounds with dithiocarbamato ligands and water-soluble phosphines of the general type [Au{κ 2 -C,NC 6 H 4 (PPh 2 =N(C 6 H 5 )-2}(S 2 CN-R 2 )]PF 6 (R = Me 2; Bz 3) and [Au{κ 2 -C,N-C 6 H 4 (PPh 2 =N(C 6 H 5 )-2}(PR 3 ) n Cl]PF 6 (PR 3 = P{Cp(m-C 6 H 4 -SO 3 Na) 2 } n = 1 4, n = 2 TPA {1,3,5-triaza-7-phosphaadamantane} 5) have been synthesized and characterized in solution and in the solid state (the crystal structure of 2 has been determined by X-ray diffraction studies). Complexes 1-5 have been tested as potential anticancer agents and their cytotoxicity properties were evaluated in vitro against HeLa human cervical carcinoma and Jurkat-T acute lymphoblastic leukemia cells. Compounds 2 and 3 are quite cytotoxic for these two cell lines. There is a preferential induction of apoptosis in HeLa cells after treatment with 1-5. However in the case of the more cytotoxic complex (2), cell death is activated due to both apoptosis and necrosis. The interactions of 1-5 with Calf Thymus DNA have been evaluated by Thermal Denaturation methods. All these complexes show no or little (electrostatic) interaction with DNA. The interaction of 2 with two model proteins (cytochrome c and thioredoxin reductase) has been analyzed by spectroscopic methods (vis-UV and fluorescence). Compound 2 manifests a high reactivity toward both proteins. The mechanistic implications of these results are discussed here.