Porphyrin donors alcohols

It is justified [32, 33] that electron demand of Fe(III) decreased by injection of electron donor substituting groups to the porphyrin ring increases the oxidation reaction rate. Moreover, it is found that at ROOH degradation alcohols and water manifest properties typical of acid catalysis. Besides epoxides, /V-alkyl hemins were detected [28], formed as a result of hemin (V-alkylation by 1-alkenes according to the following reaction [34, 35] ... 

Irradiation of alcohol solutions of Mn(acac)20C0Cp3 and Mn(acac)3 leads to formation of the bis(acac) complex of Mn". E.s.r. examination revealed that the products arise by reduction of the central metal ion. Visible light irradiation of Mn TMPyP [TMPyP = tetrakis-(4-methylpyridyl)porphyrin] in aqueous solution containing EDTA or triethanolamine as an electron donor gives rise to the formation of Mn TMPyP. The light-induced redox cheirac-teristics of Mn °TMPyP in the presence of methyl viologen (MV ) and electron donors has also been described. ... 

Mansuy et al. employed alkyl peroxides and iodosylbenzene as oxygen donors and examined the oxidation products of cyclohexane in the presence of a series of M(TPP) complexes (M=Fe, Mn, Co, Rh, and Cr) [284]. As listed in Table 10, cyclohexanol and cyclohexanone are the major products however, the ratio of the alcohol and ketone was dependent on the oxidant employed. For the oxidation by peroxides, involvement of alkoxy radical (RO ) due to the homolytic 0-0 bond cleavage of R-OO-M was proposed. In order to trap possibly formed radical intermediates. He and Bruice examined the oxidation of cw-stilbene and (Z)-l,2-bis(fran5-2,tran5-3-diphenylcyclopropyl)ethane by iron porphyrin/f-BuOOH system [285]. In separate experiments, AIBN was used as a radical chain initiator for the oxidation of the alkenes by t-BuOOH. According to the product distribution, they concluded the products to be derived from initial combination of t-BuOO, rather than 0=Fe (por)", with olefin. 

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