期刊
POLYHEDRON
卷 67, 期 -, 页码 51-58出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2013.08.057
关键词
Speciation; Stability constants; Antitumor agents; Picolinic acid; Dipicolinic acid
资金
- Hungarian Research Foundation [OTKA 103905]
- J. Bolyai research fellowship
- European Social Fund
Stoichiometry and stability of antitumor ruthenium(II)-eta(6)-p-cymene complexes of picolinic acid and its 6-methyl and 6-carboxylic acid derivatives were determined by pH-potentiometry, H-1 NMR spectroscopy and UV-Vis spectrophotometry in aqueous solution in the presence or absence of coordinating chloride ions. The picolinates form exclusively mono-ligand complexes in which they can coordinate via the bidentate (0,N) mode and a chloride or a water molecule is found at the third binding site of the ruthenium(11)-eta(6)-p-cymene moiety depending on the conditions. [Ru(eta(6)-p-cymene)(L)(H2O/Cl)) species are predominant at physiological pH in all studied cases. Hydrolysis of the aqua complex or the chlorido/ hydroxido co-ligand exchange results in the formation of the mixed-hydroxido species [Ru(eta(6)-p-cymene)(L)(OH)] in the basic pH range. There is no indication for the decomposition of the mono-ligand complexes during 24h in the ruthenium(II)-eta(6)-p-cymene-picolinic acid system between pH 3 and 11; however, a slight dissociation with a low reaction rate was found in the other two systems leading to the appearance of the dinuclear trihydroxido-bridged species [Ru-2(eta(6)-p-cymene)(2)(OH)(3)](+) and free ligands at pH > 10. The replacement of the chlorido by an aqua ligand in [Ru(eta(6)-p-cymene)(L)Cl) was also monitored and equilibrium constants for the exchange process were determined. (C) 2013 Elsevier Ltd. All rights reserved.
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