Speciation and structure of tin(II) in hyper-alkaline aqueous solution.

The identity of the predominating tin(ii)-hydroxide complex formed in hyper-alkaline aqueous solutions (0.2 ≤CNaOH≤ 12 mol dm(-3)) is determined by potentiometric titrations, Raman, Mössbauer and XANES spectroscopy, supplemented by quantum chemical calculations. Thermodynamic studies using a H2/Pt electrode up to free hydroxide concentrations of 1 mol dm(-3) showed the presence of a single monomeric complex with a tin(II) : hydroxide ratio of 1 : 3. This observation together with Raman and Mössbauer spectroscopic measurements supplemented by quantum mechanical calculations proved that the predominating complex is [Sn(OH)3](-), and that the presence of the other possible complex, [SnO(OH)](-), could not be proven with either experiments or simulations. The structure of the trihydroxidostannate(II) complex, [Sn(OH)3](-), was determined by EXAFS and was found to be independent of the applied hydroxide and tin(II) concentrations. The mean Sn-O bond distance is short, 2.078 Å, and in very good agreement with the only structure reported in the solid state. It is also shown that at pH values above 13 the speciation of the predominant trihydroxidostannate(II) complex is not affected by the presence of high concentrations of chloride ions.

Multinuclear complex formation in aqueous solutions of Ca(II) and heptagluconate ions.

The equilibria and structure of complexes formed between the Ca(2+) ion and the heptagluconate (Hglu(-)) ion in both neutral and alkaline solutions have been studied. In alkaline solutions an uncharged, multinuclear complex is formed with the composition of Ca3Hglu2(OH)4 (or [Ca3Hglu2H(-4)](0)) with an unexpectedly high stability constant (lg ß(32-4) = 14.09). The formation of the trinuclear complex was deduced from potentiometry and confirmed by freezing-point depression measurements and conductometry as well. The binding sites of Hglu(-) were determined from NMR measurements. Besides the carboxylate group, the O atoms on the second and third carbon atoms proved to be the most probable sites for Ca(2+) binding.

Biological activity and coordination modes of copper(II) complexes of Schiff base-derived coumarin ligands.

The coordination modes of copper(II) complexes of Schiff base-derived coumarin ligands, which had previously shown good anti-Candida activity, were investigated by pH-potentiometric and UV-Vis spectroscopic methods. These studies confirmed the coordination mode of the ligands to be through the N of the imine and deprotonated phenol of the coumarin-derived ligand in solution. In addition, the more active complexes and their corresponding ligands were investigated in the presence of copper(II) in liquid and frozen solution by ESR spectroscopic methods. A series of secondary amine derivatives of the Schiff base ligands, were isolated with good solubility characteristics but showed little anti-Candida activity. However, cytotoxicity studies of the secondary amines, together with the copper complexes and their corresponding ligands, against human colon cancer and human breast cancer cells identified the chemotherapeutic potential of these new ligands.