Abstract
AbstractThe oxidative behaviour and relative reactivities of three alkanols and 11 aryl alcohols towards gold(III) in sodium acetate–acetic acid buffer were studied. The reactions are first order with respect to [Au(III)] and in each [R1R2CHOH]. Both H+ and Cl− ions retard the rate of reactions. The reactions obey the following rate expression: AuCl4−, AuCl3(OH2) and AuCl3(OH)− are the reactive species of gold(III) and the reactivity follows the order AuCl3(OH)− > AuCl3(OH2) > AuCl4−. The activation parameters of the reactions were calculated. Alkanols react with gold(III) in the order ethanol > methanol > 2‐propanol. The unsubstituted benzyl alcohol reacts with gold(III) at a faster rate than benzhydrol. The pseudo‐first‐order rate constants in the oxidations of aryl alcohols follow the order NO2 > H > Cl > OMe. The reactions occur via C—H bond cleavage and through the intermediate formation of free radicals. Copyright © 2001 John Wiley & Sons, Ltd.
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