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Kinetics of oxidation of pyruvic acid by [ethylenebis(biguanide)]silver(III) in aqueous acidic media

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Abstract

The oxidation of pyruvic acid by the title silver(III) complex in aqueous acidic (pH, 1.1–4.5) media is described. The reaction products are MeCO2H and CO2, together with a colourless solution of the Ag+ ion. The free ligand, ethylenebis(biguanide) is released in near-quantitative yield upon completion of the reduction. The parent complex, [Ag(H2L)]3+ and one of its conjugate bases, [Ag(HL)]2+, participate in the reaction with both pyruvic acid (HPy) and the pyruvate anion (Py−) as the reactive reducing species. Ag+ was found to be catalytically inactive. At 25.0°C, I=1.0moldm−3, rate constants for the reactions [Ag(H2L)]3++HPy (k 1), [Ag(H2L)]3++Py− (k 2), [Ag(HL)]2++HPy (k 3) and [Ag(HL)]2++Py− (k 4) arek 1=(94±6)×10−5dm3mol−1s−1, (k 2 K a+k 3 K a1)= (1.3±0.1)×10−5s−1 and k 4=(58±4)×10−5dm3mol−1s−1, respectively, where K a1is the first acid dissociation constant of the [Ag(H2L)]3+ and K a is for pyruvic acid. A comparison between the k 1 and k 4 values is indicative of the judgement that k 2≫k 3. A one-electron inner-sphere redox mechanism seems more justified than an outer-sphere electron-transfer between the redox partners.

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  1. Department of Chemistry, Jadavpur University, Calcutta, 700 032, India

    Amit Das & Subrata Mukhopadhyay

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  1. Amit Das
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Das, A., Mukhopadhyay, S. Kinetics of oxidation of pyruvic acid by [ethylenebis(biguanide)]silver(III) in aqueous acidic media. Transition Metal Chemistry 29, 797–803 (2004). https://doi.org/10.1007/s11243-004-1015-9

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