Cationic Metalloporphyrins Imobilized in Faujasite Zeolites as a Cytochrome P-450 Mimic

Luciana P. B. Lôvo, Fabiana C. Skrobot, Gianluca C. Azzellini, Yassuko Iamamoto, Ieda L. V. Rosa

Departamento de Química, FFCLRP, Universidade de S?o Paulo, Ribeir?o Preto, Brazil.
Departamento de Química, Universidade Federal de S?o Carlos, S?o Carlos, Brazil.
Instituto de Química, Universidade de S?o Paulo, S?o Paulo, Brazil.

DOI: 10.4236/mrc.2013.22008                

Abstract

Metalloporphyrins immobilized into NaY zeolite are described as catalysts for hydrocarbon oxyfuntionalization. Manganese(III) and iron(III)tetrakis(4-N-methylpyridyl)-porphyrin (MnP1 and FeP1), and manganese(III) and iron(III) tetrakis(4-N-benzylpiridil)-porphyrin (MnP2 and FeP2) were impregnated (MnP1-NaY_imp, FeP1-NaY_imp, MnP2-NaY_imp, FeP2-NaY_imp, respectively) and encapsulated (MnP1-NaY, FeP1-NaY, MnP2-NaY and FeP2-NaY) into the NaY zeolite. These catalysts were used in the oxidation of (Z)-cyclooctene, cyclohexane, and adamantane by iodosylbezene (PhIO). These systems were able to epoxidize (Z)-cyclooctene with cis-epoxycyclooctane yields as high as 100%. By using cyclohexane and adamantane as substrate, the susceptibility of the benzyl groups on the porphyrin ring of the MnP materials, led to a different distribution of the oxidized products. With FePs, this susceptibility was not detected because the species responsible for the oxidations, Fe^IV(O)P^·+, is more active than Mn^V(O)P. In conclusion, cationic metalloporphyrins immobilized into NaX zeolites, are good cytochrome P-450 models is less polar solvents since the selectivity of the system indicates the “in cage” solvent oxygen rebound oxidative process.

Keywords

Metalloporphyrin; Iodosylbenzene; Hydrocarbon Oxidation; Y Zeolite

Conflicts of Interest

The authors declare no conflicts of interest.

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