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

• 作者: Fabiana C. Skrobot Gianluca C. Azzellini Ieda L. V. Rosa Luciana P. B. L?vo Yassuko Iamamoto
• 来源期刊: 催化剂现代研究(英文)
• 学科: 化学
• 关键词: METALLOPORPHYRIN IODOSYLBENZENE Hydrocarbon Oxidation Y ZEOLITE
• 年，卷（期）: 2013,（2）
• 页码范围: 47-55
• 页数: 9页
• 分类号: O6

摘要

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-NaYimp, FeP1-NaYimp, MnP2-NaYimp, FeP2-NaYimp, 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, FeIV(O)P·+, is more active than MnV(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.