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Mechanism of Ruthenium (III) Catalysis of Periodate Oxidation of Aldoses in Aqueous Alkaline Medium

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Abstract

A general mechanism for Ru(III) catalysed oxidation of L(+) arabinose (Ara) and D(+) galactose (Gal) in aqueous alkaline medium is proposed. The most reactive species of the catalyst was found to be [RuCl3(OH)2H2O]2−. The reactions exhibit pseudo-first order kinetics with respect to Ru(III) and are first order with respect to lower [IO4 −] and OH−, but tend towards zeroth order to both higher [IO4 −] and [OH−]. The reactions are zero order with respect to each aldoses. Positive effect of Cl− on the rate of reaction is also evident in the oxidation of both reducing sugars. A mechanism, involving the interaction of the reactive species of Ru(III) and [IO4 −] leading to the formation of a complex, which in the rate determining step decomposes into another complex with the release of Cl− ion, is proposed and the rate law is derived.

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Authors and Affiliations

  1. Department of Chemistry, University of Allahabad, Allahabad, 211002, India

    Ashok Kumar Singh, N. Chaurasia, Shahla Rahmani, Jaya Srivastava & Bharat Singh

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  1. Ashok Kumar Singh
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  2. N. Chaurasia
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  3. Shahla Rahmani
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  4. Jaya Srivastava
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  5. Bharat Singh
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Correspondence to Ashok Kumar Singh.

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Singh, A.K., Chaurasia, N., Rahmani, S. et al. Mechanism of Ruthenium (III) Catalysis of Periodate Oxidation of Aldoses in Aqueous Alkaline Medium. Catalysis Letters 95, 135–141 (2004). https://doi.org/10.1023/B:CATL.0000027286.07404.48

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