Kinetics and mechanism of the oxidation of neutralized α-hydroxy acids by tris(pyridine-2-carboxylato)manganese(III)

The kinetics of oxidation of the neutralized α-hydroxy acids: lactic, α-hydroxyisobutyric, mandelic, benzilic and atrolactic acids by tris(pyridine-2-carboxylato)manganese(III) have been studied. The reactions were carried out in a Na(pic)-picH [Na(pic) = sodium salt of pyridine-2-carboxylic acid and picH = pyridine-2-carboxylic acid] buffer medium in the 4.89–6.10pH range. The oxidation rate was found to be independent of pH, and rate follows the order: benzilate > mandelate >atrolactate>lactate > α-hydroxy isobutyrate. The oxidation products are MeCHO, Me2CO, PhCHO, Ph2CO and PhCOMe for the respective reactions. A mechanism is proposed involving intermediate formation of hepta-coordinated MnIII complexes in a fast step. The complexes then decompose to give free radicals and MnII in the rate determining step. The free radicals subsequently react with another molecule of the MnIII species to give the respective carbonyl compounds in a fast step.