Alcohol oxidation catalysed by Ru(VI) in the presence of alkaline hexacyanoferrate(III)

摘要

The oxidation of sodium lactate, 2-methyl-2,4-pentanediol, 2,4-butanediol, 2-butanol and 2-propanol upon treatment with alkaline hexacyanoferrate(III) using a Ru(VI) catalyst is highly effective for the oxidation of alcohols by Fe(CN)_63-. The reaction mechanism proposed involves the oxidation of the alcohol 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 carbocation (owing to a hydride transfer from the α-C-H bond of the alcohol to the oxoligand of ruthenium). The role of the co-oxidant, hexacyanoferrate(III), is to regenerate the catalyst. In the oxidation reactions, the rate constants for complex decomposition and catalyst regeneration have been determined and a comparative study of the structure versus reactivity has been carried out.