Cationic iroporphyrins as catalyst in comparative oxidation of hydrocarbons: homogeneous and supported on inorganic matrices systems
โ Scribed by Yassuko Iamamoto; Ynara Marina Idemori; Shirley Nakagaki
- Book ID
- 103997463
- Publisher
- Elsevier Science
- Year
- 1995
- Tongue
- English
- Weight
- 711 KB
- Volume
- 99
- Category
- Article
- ISSN
- 1381-1169
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โฆ Synopsis
Cationic ironporphyrins in solution and supported on imidazole propyl gel (IPG) and silica gel (SC) as catalyst in cyclohexane hydroxylation using iodosylarene as oxygen donor were studied. FeTM4Pyp+ 1 as homogeneous catalyst for cyclohexane hydroxylation, in acetonitrile (CH,CN) and ultrasound stirring, gives cyclohexanol (C-01) yields of 20%. The FeTM2PyP5 + 2 as catalyst for cyclohexene oxidation in CH$N and ultrasound stirring is a very efficient system, giving 93% of total yield, with an epoxide:alcohol:ketone selectivity of 77: 12: 11. The supported systems, l-IPG and l-SG are particularly efficient in dichloromethane (CH,Cl,), giving C-01 yields of 37% and 53%, respectively. These systems consist of polar hemin in isolated sites, which selectively catalyze cyclohexane oxidation in apolar solvent. They represent good cytochrome P-450 model systems. In the same way, the active site of P-450 consists of a polar protohemin in a hydrophobic pocket, promoting selective cyclohexane oxidation. These rigid cationic l-IPG, l-SG, ZIPG, 2-SG, 3-IPG and 3-SG systems can catalyze with very small amounts of ironporphyrins, which correspond to about 30-80 times fewer numbers than the hemin in P-450 catalytic site.
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