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Kinetics and mechanism of base hydrolysis of chromium(III) complexes with oxalates and quinolinic acid

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Abstract

Base hydrolysis of [Cr(ox)2(quin)]3− (where quin2− is N,O-bonded 2,3-pyridinedicarboxylic acid dianion) causes successive ligand dissociation and leads to a formation of a mixture of oligomeric chromium(III) species, known as chromates(III). The reaction proceeds through [Cr(ox)(quin)(OH)2]3− and [Cr(quin)(OH)4]3− formation. Dissociation of oxalato ligands is preceded by the opening of the Cr-quin chelate-ring at the Cr–N bond. The kinetics of the chelate-ring opening and the first oxalate dissociation were studied spectrophotometrically, within the lower energy d–d band region at 0.4–1.0 M NaOH. The pseudo-first-order rate constants (k obs0 and k obs1) were calculated using SPECFIT software for an A → B → C reaction pattern. Additionally, kinetics of base hydrolysis of [Cr(ox)(quin)(OH)2]3− and cis-[Cr(ox)2(OH)2]3− were studied. The determined pseudo-first-order rate constants were independent of [OH−]. A mechanism is postulated that the reactive intermediate with the one-end bonded quin ligand, [Cr(ox)2(O-quin)(OH)]4−, formed in the first reaction stage, subsequently undergoes oxalates substitution. Kinetic parameters for the chelate-ring opening and the first oxalate dissociation were determined.

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Acknowledgments

Hasan Marai thanks Libyan Government for financial support of his Ph.D. studies in Poland.

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  1. Department of Chemistry, Nicolaus Copernicus University, 87-100, Toruń, Poland

    Ewa Kita & Hasan Marai

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  1. Ewa Kita
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  2. Hasan Marai
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Correspondence to Ewa Kita.

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Kita, E., Marai, H. Kinetics and mechanism of base hydrolysis of chromium(III) complexes with oxalates and quinolinic acid. Transition Met Chem 34, 585–591 (2009). https://doi.org/10.1007/s11243-009-9234-8

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