Oxidations by the system 'hydrogen peroxide-[Mn2L2O3][PF6]2 (L=1,4,7-trimethyl-1,4,7-triazacyclononane)-carboxylic acid'.: Part 10:: Co-catalytic effect of different carboxylic acids in the oxidation of cyclohexane, cyclohexanol, and acetone

Hydrogen peroxide oxidation of cyclohexane in acetonitrile solution catalyzed by the dinuclear manganese(IV) complex [LMn(O)(3)MnL](PF6)(2) (L=1,4,7-trimethyl-1,4,7-triazacyclononane, TMTACN) at 25 degrees C in the presence of a carboxylic acid affords cyclohexyl hydroperoxide as well as cyclohexanone and cyclohexanol. A kinetic study of the reactions with participation of three acids (acetic acid, oxalic acid, and pyrazine-2,3dicarboxylic acid, 2,3-PDCA) led to the following general scheme. In the first stage, the catalyst precursor forms an adduct. The equilibrium constants K, calculated for acetic acid, oxalic acid, and 2,3-PDCA were 127 +/- 8, (7 +/- 2) x 10(4), and 1250 +/- 50 M-1, respectively. The same kinetic scheme was applied for the cyclohexanol oxidation catalyzed by the complex in the presence of oxalic acid. The oxidation of cyclohexane in water solution using oxalic acid as a co-catalyst gave cyclohexanol and cyclohexanone, which were rapidly transformed into a mixture of over-oxidation products. In the oxidation of cyclohexanol to cyclohexanone, varying the concentrations of the reactants and the reaction time we were able to find optimal conditions and to obtain the cyclohexanone in 94% yield based on the starting cyclohexanol. Oxidation of acetone to acetic acid by the system containing oxalic acid was also studied. (c) 2007 Elsevier Ltd. All rights reserved.