Cuprous Complexes and Dioxygen. Part 12.. Rate law and mechanism of the copper-catalyzed oxidation of ascorbic acid in aqueous acetonitrile |
| |
Authors: | Li Mi,Andreas D. Zuberbü hler |
| |
Abstract: | The copper-catalyzed oxidation of ascorbic acid (AscH2) has been studied with a Clark electrode in aqueous MeCN. CuI or CuII may be equally used as the source of metal ion, without influence on the rate law. At sufficiently high [MeCN], the rate of the overall reaction is essentially given by the rate of CuI autoxidation: the reaction is of first order with respect to [Cu] and [O2] and shows an inverse-square dependence on [MeCN] as observed for the autoxidation of Cu. The pH dependence is complicated by the combination of the intrinsic pH effect on autoxidation with an additional term in the rate law which is directly proportional to [AscH?]. The latter term is explained by direct oxidation of the organic substrate by the primary dioxygen adduct of CuI, CuO. For [MeCN] < 0.7M , a gradual and pH-dependent transformation of this rate law and deviation from the first-order dependence on [O2] is indicated. |
| |
Keywords: | |
|
|