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Mixed chromium(III) complexes with pyridinedicarboxylato and oxalato ligands: kinetic studies in HClO4 solutions

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Abstract

Three chromium(III) complexes of general formula [Cr(ox)2(pdaH)]2− (where ox = C2O4 2− and pdaH is N,O-bonded 2,3-, 2,4- or 2,5-pyridinedicarboxylic acid anion) were obtained and characterized in solution. Acid-catalysed aquation of [Cr(ox)2(pdaH)]2− gave two products: [Cr(ox)(pdaH)(H2O)2]0 (P1) and cis-[Cr(ox)2(H2O)2]2− (P2). The kinetics of these reactions were studied spectrophotometrically, within the 0.1–1.0 M HClO4 range, and the pseudo-first-order rate constants for the oxalato (k obs1) and pdaH (k obs2) ligands dissociation were calculated based on the determined pseudo-first-order rate constants (k obs) and P1:P2 molar ratio. The dependencies of the pseudo-first-order rate constants on [H+] are as follows: k obs1 = b 1[H+] and k obs2 = b 2[H+], where b 1 and b 2 are the second-order rate constants for the oxalato and pdaH ligands dissociation, respectively. Kinetic parameters were determined and the mechanism of the pdaH ligand dissociation is proposed.

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Acknowledgements

(i) The authors wish to thank authorities of N. Copernicus University for the financial support of these studies with the Grant No. 368-Ch; (ii) Hasan Marai wishes to thank Libyan Government for financial support of his Ph.D. studies in Poland.

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Correspondence to Ewa Kita.

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Kita, E., Marai, H., Jach, K. et al. Mixed chromium(III) complexes with pyridinedicarboxylato and oxalato ligands: kinetic studies in HClO4 solutions. Transition Met Chem 34, 217–224 (2009). https://doi.org/10.1007/s11243-008-9181-9

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