Synthesis, characterization and antitumor activity of palladium(II) complexes of monoethyl 8-quinolylmethylphosphonate

The complex-forming properties of monoethyl 8-quinolylmethylphosphonate (8-Hmqmp) towards palladium(II) ion have been investigated by reactions of the hydrochloride, 8-Hmqmp center dot HCl center dot H2O, and sodium salt, Na(8-mqmp).2H(2)O, of this monoester with palladium(II) halide compounds in aqueous solution over a wide pH range. Depending on pH and initial quinolinium and palladium salts, four types of complexes have been formed. Under acidic solution the ion-pair salt complexes [8-H(2)mqmp](2)[PdX4] (1 and 2, pH < 3) and [8-H(2)mqmp](2)[Pd2X6](3 and 4, pH similar to 3), with protonated quinoline ligand as cation and tetrahalopalladate or hexahalodipalladate complex as anion (X = Cl, Br), were isolated. By heating in methanol the chloro complexes 1 and 3 as well as bromo complexes 2 and 4 were converted into the quinolinium salt complexes, [8-H(2)mqmp][Pd(8-Hmqmp)X-3], 5 and 6, respectively, containing as anion the quinol oliniummethylphosphonatetrihalopalladate complex with palladium bonded at the phosphonic acid moiety. The chelate complex 7, [Pd(8-mqmp)(2)], with ligand bonded through the quinoline nitrogen and the deprotonated phosphonic acid oxygen and forming two seven-membered {N,O} chelate rings, was obtained in neutral and basic media. The complexes were identified and characterized by elemental analysis, magnetic and conductance measurements, spectroscopic studies (IR, H-1 NMR, UV-Vis, positive/negative ion FAB MS) and thermal analysis (TG, DTA). As a preliminary screening for their biological activity, complexes were investigated for their ability to inhibit the cancer growth in vitro in the human KB and murine L1210 cell lines. The results obtained were compared with those obtained for the complexes of diethyl 8-quinolylmethylphosphonate (8-dqmp) and monoethyl 2-quinolylmethylphosphonate (2-Hmqmp), and structural factors that determine the complex activity were discussed. (c) 2008 Elsevier Ltd. All rights reserved.