The oxidation reactions of 2-methyl-2,4-pentanediol upon treatment with alkaline hexacyanoferrate(III) using Ru(III) or Ru(VI) as catalysts are governed by two quasi-identical experimental rate equations, which show that both catalysts are equally effective for the oxidation of alcohols by . The reaction mechanism proposed involves the oxidation of 2-methyl-2,4-pentanediol by the catalyst, a process that occurs through the formation of a substrate–catalyst complex. The decomposition of this complex yields Ru(IV) and a protonated ketone (owing to a hydride transfer from the α-C—H bond of the alcohol to the oxoligand of ruthenium) in the case of Ru(VI), but a ketyl radical and Ru(II) (hydrogen transfer) for Ru(III). The role of the co-oxidant, , is to regenerate the catalyst. For both oxidation reactions, the rate constants of complex decomposition and catalyst regeneration have been determined. Copyright © 2004 John Wiley & Sons, Ltd.