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Kinetics and mechanism of periodate oxidation of two ternary nitrilotriacetatochromium(III) complexes involving histidine and aspartate co-ligands

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Abstract

The oxidation of [CrIII(HNTA)(Hist)(H2O)]− and [CrIII(HNTA)(Asp)(H2O)]− (NTA = nitrilotriacetate, Hist = l-histidinate and Asp = dl-aspartate) by periodate in aqueous medium has been studied spectrophotometrically between 15.0 and 35.0 °C under pseudo-first-order conditions, [IO4 −] ≫ [complex]. The rate increases over the pH range 3.40–4.45 in both cases, but the two complexes give different rate laws. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4 − to chromium(III). A common mechanism for the oxidation of some chromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions.

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Authors and Affiliations

  1. Chemistry Department, Faculty of Science, El-Kamel Branch, King Abdulaziz University, Jeddah, Saudi Arabia

    Hassan A. Ewais & Shabaan A. K. Elroby

  2. Chemistry Department, Faculty of Science, Al-Tahadi University, Serit, Lybia

    Mohamed A. Habib

Authors
  1. Hassan A. Ewais
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  2. Mohamed A. Habib
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  3. Shabaan A. K. Elroby
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Corresponding author

Correspondence to Hassan A. Ewais.

Additional information

Abstract is from the M.Sc thesis of Mohamed A. Habib.

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Ewais, H.A., Habib, M.A. & Elroby, S.A.K. Kinetics and mechanism of periodate oxidation of two ternary nitrilotriacetatochromium(III) complexes involving histidine and aspartate co-ligands. Transition Met Chem 35, 73–80 (2010). https://doi.org/10.1007/s11243-009-9297-6

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