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Chromium(III)-isonicotinate Complexes. Kinetics and Mechanism of Isonicotinate Ligand Liberation in HClO4 Solutions

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Abstract

Chromium(III)-isonicotinate complexes, cis-[Cr(C2O4)2(N-inic)(H2O)]- and [Cr(C2O4)(H2O)3-OH-Cr(C2O4)2(O-inic)]-(N-inic)(H2 (N-inic = N-bonded and O-inic = O-bonded isonicotinic acid) were obtained and characterized in solution. Kinetics of acid-catalyzed isonicotinate ligand liberation were studied spectrophotometrically in the 0.1–1.0 m HClO4 range, at I=1.0 m. The dependencies of the pseudo-first order rate constant on [H+] were established: kobs = k0+kHQH[H+] and kobs = kHQH[H+] for the N-inic and O-inic complex, respectively, where k0 and kH are the rate constants of the spontaneous and the acid-catalyzed reaction paths, and QH is the protonation constant of the carboxylic group in isonicotinic ligand. The obtained results indicate that N-bonded isonicotinic acid liberation occurs mainly via a spontaneous reaction path and is much slower than O-bonded inic liberation. The mechanisms for these processes are proposed.

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

    Małgorzata Szabłowicz & Ewa Kita

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  1. Małgorzata Szabłowicz
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  2. Ewa Kita
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Correspondence to Ewa Kita.

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Szabłowicz, M., Kita, E. Chromium(III)-isonicotinate Complexes. Kinetics and Mechanism of Isonicotinate Ligand Liberation in HClO4 Solutions. Transition Met Chem 31, 220–226 (2006). https://doi.org/10.1007/s11243-005-6385-0

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  • DOI: https://doi.org/10.1007/s11243-005-6385-0

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