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• W2029401952 abstract "The complex cation, [ethylenebis(biguanide)]silver(III), [Ag(H2L)]3+, and its conjugate bases, [Ag(HL)]2+ and [AgL]+ oxidise glyoxylic acid, CHOCO2H quantitatively to formic acid and carbon dioxide, themselves being reduced to Ag+. Free ethylenebis(biguanide) was recovered in near-quantitative yield. In the investigated pH range (1.00–7.00), the reaction is first order in both [complex] and total glyoxylate, [HGX]T. The reaction proceeds through four parallel paths: [Ag(H2L)]3+ – HGX (k1), [Ag(H2L)]3+ – GX− (k2), [Ag(HL)]2+ – GX− (k3), and [AgL]+ – GX− (k4). The respective rate constants (in 104 M−1 s−1) are, respectively, 7.34, 112, 40.7 and 19.2 at 25.0 °C and I=1.0 M (NaNO3). Formation of adducts by the reducing species with the metal complex via hydrogen-bonding or electrostriction may be proposed for the low-energy pathway for electron-transfer. A substantial rate retardation in presence of the radical scavenger acrylonitrile suggests successive one-electron changes, AgIII → AgII → AgI." @default.
• W2029401952 created "2016-06-24" @default.
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• W2029401952 date "2004-03-01" @default.
• W2029401952 modified "2023-09-23" @default.
• W2029401952 title "Kinetics of oxidation of glyoxylic acid by [ethylenebis(biguanide)]silver(III) in aqueous media" @default.
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• W2029401952 doi "https://doi.org/10.1016/j.poly.2003.12.006" @default.
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