The mechanistic aspects of iron(III) porphyrin catalyzed oxidation reactions in mixed solvents

Abstract

In the iron(III) porphyrin catalyzed oxidation reactions, the formation of various reactive intermediates have been observed to depend upon the nature of the catalyst, the oxidant and the solvent used for the study. The various iron(III) porphyrin catalysts such as F 20TPPFeCl, F 16TPPFeCl, F 12TPPFeCl and F 8TPPFeCl have been used in the present study to understand the effect of solvent system in the activation of the catalysts. As the terminal oxidant t-BuOOH has been used. It has been observed that acetonitrile contaminated with water activates all the catalysts. It has been noted that ∼9% of water in acetonitrile is the best solvent system for the activation of all the catalysts. The results obtained have been applied to successfully oxidize cyclohexene and cyclohexane by these oxidizing systems. It has also been observed that CH 3OH mixed with CH 2Cl 2 play a very important role in the activation of catalyst in hydroperoxide oxidizing system. The 33 ± 3% ratio of CH 3OH in CH 2Cl 2 acts as the most suitable solvent system to convert organopalladium compound 1a– c to 2a– c.