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Kinetic studies on H+-catalysed aquation of chromium(III)-oxalato-asparaginato and chromium(III)-oxalato-histidinato complexes

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Abstract

Three chromium(III) complexes with asparagine (Asn) and histidine (His) of the [Cr(ox)2(Aa)]2− type, where Aa = N,O–Asn, N,O–His or N,N′–His, were obtained and characterized in solution. The complexes with N,O–Aa undergo acid-catalysed aquation to give a free amino acid and cis-[Cr(ox)2(H2O)2], whereas the complex with N,N′–His undergoes parallel reaction paths: (1) isomerization to the N,O–His complex and (2) liberation of an oxalate ligand. Kinetics of the N,O–Aa complexes in HClO4 media were studied spectrophotometrically under pseudo-first-order conditions. The absorbance changes were attributed to the chelate ring opening at the Cr–N bond. The linear dependence of rate constants on [H+] was established, and a mechanism for the chelate ring cleavage was postulated. The existence of a metastable intermediate with O-monodentate Aa ligand was proved experimentally. Effect of [Cr(ox)2(Aa)]2− on 3T3 fibroblasts proliferation was studied. The tests revealed low cytotoxicity of the complexes. Complexes with Ala, His and Cys are good candidates for biochromium sources.

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Marai, H., Kita, E., Kiersikowska, E. et al. Kinetic studies on H+-catalysed aquation of chromium(III)-oxalato-asparaginato and chromium(III)-oxalato-histidinato complexes. Transition Met Chem 37, 337–344 (2012). https://doi.org/10.1007/s11243-012-9594-3

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  • DOI: https://doi.org/10.1007/s11243-012-9594-3

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