Kinetics of the Oxidation of 2,3-Dimethylbutane-2,3-diol by Bis(2,2'-bipyridine)silver(II) Ions in Aqueous Nitrate Media

DOI: 10.1039/f19848002155

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 2155 - 2166 (1984)

Update date:2022-08-28

Topics:

Authors:

Heyward, Malcolm P.

Wells, Cecil F.

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Article abstract of DOI:10.1039/f19848002155

The stoichiometry and the kinetics of the oxidation of 2,3-dimethylbutane-2,3-diol (pinacol) by (2+) ions have been investigated.It is shown that the oxidation proceeds through intermediate complexes involving Ag(II) and pinacol.Although (2+) itself is eliminated as a participant in these oxidatively active complexes, (2+) remains as a possible intermediate.The kinetics show that one of the principal pathways involves Ag(aq)(2+) complexed with un-ionised pinacol, but they do not distinguish between the involvement of (2+) and in the order principal path: the linear Arrhenius plots suggest that the latter two are alternatives and not parallel courses.Values for the enthalpies and entropies of activation are determined.This oxidation is compared with the oxidation of other substrates by (2+); the pathway involving oxidation by Ag(2+) with all the bipyridine removed is compared with the oxidation of other substrates by Ag(aq)(2+) and the oxidation of pinacol and other substrates by other aquacations.