Mechanism of Alkene, Alkane, and Alcohol Oxidation with H₂O₂ by an in Situ Prepared Mn^II/Pyridine-2-carboxylic Acid Catalyst

Abstract

The oxidation of alkenes, alkanes, and alcohols with H 2 O 2 is catalyzed efficiently using an in situ prepared catalyst comprised of a Mn II salt and pyridine-2-carboxylic acid (PCA) together with a ketone in a wide range of solvents. The mechanism by which these reactions proceed is elucidated, with a particular focus on the role played by each reaction component: i.e., ketone, PCA, Mn II salt, solvent, etc. It is shown that the equilibrium between the ketone cocatalysts, in particular butanedione, and H 2 O 2 is central to the catalytic activity observed and that a gem -hydroxyl-hydroperoxy species is responsible for generating the active form of the manganese catalyst. Furthermore, the oxidation of the ketone to a carboxylic acid is shown to antecede the onset of substrate conversion. Indeed, addition of acetic acid either prior to or after addition of H 2 O 2 eliminates a lag period observed at low catalyst loading. Carboxylic acids are shown to affect both the activity of the catalyst and the formation of the gem -hydroxyl-hydroperoxy species. The molecular nature of the catalyst itself is explored through the effect of variation of Mn II and PCA concentration, with the data indicating that a Mn II:PCA ratio of 1:2 is necessary for activity. A remarkable feature of the catalytic system is that the apparent order in substrate is 0, indicating that the formation of highly reactive manganese species is rate limiting.