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New chromium(III)–picolinamide complexes. Kinetics and mechanism of picolinamide liberation in HClO4 solutions

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Abstract

Two new chromium(III) complexes with picolinamide (pica) and oxalates, [Cr(C2O4)2(N,N′-pica)]2− and [Cr(C2O4)2(N,O-pica)]−, were obtained and the kinetics of their aquation in HClO4 solutions were studied. The aquation leads to pica liberation and proceeds in two stages: (i) the chelate-ring opening at the Cr–amide bond and (ii) the Cr–N-pyridine bond breaking, which gives free pica and cis-[Cr(C2O4)2(H2O2)2]−. In the case of N,N′-bonded pica the kinetics of both stages was determined and in the case of the N,O-bonded pica only the second stage was investigated. The following rate laws were established: (k obs)1 = k 0  +  k 1 Q 1[H+] and (k obs)2 = k 2 Q 2[H+], where k 0 and k 1 are the rate constants of the chelate-ring opening in the unprotonated and protonated starting complex, and k 2 is the rate constant of the pica liberation from the protonated intermediate. Kinetic parameters are calculated and the aquation mechanism is discussed.

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Authors and Affiliations

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

    Małgorzata Pazderska-Szabłowicz, Adam Karpiński & Ewa Kita

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  1. Małgorzata Pazderska-Szabłowicz
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  2. Adam Karpiński
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  3. Ewa Kita
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Correspondence to Ewa Kita.

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Pazderska-Szabłowicz, M., Karpiński, A. & Kita, E. New chromium(III)–picolinamide complexes. Kinetics and mechanism of picolinamide liberation in HClO4 solutions. Transition Met Chem 31, 1075–1080 (2006). https://doi.org/10.1007/s11243-006-0113-2

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  • DOI: https://doi.org/10.1007/s11243-006-0113-2

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