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Авдеев, М. В.; Bagrii, E. I.; Maravin, G. B.; Korolev, Yu. M.

doi:10.1023/a:1014240927361

Cited by 11 publications

(2 citation statements)

References 3 publications

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“…In the last two decades, oxidation of hydrocarbons catalyzed by metalloporphyrins under mild conditions has attracted much interest because of their potential application and the environmentally friendly conditions [21][22][23][24][25][26][27]. A large class of synthetic metalloporphyrins was used as catalysts for the oxidation of saturated C-H bond, C-C double bonds and aromatics [28][29][30][31][32][33][34][35]. Our group has reported that metalloporphyrins could catalyze effectively the oxidation of cyclohexane [36] and toluene [37] with air in the absence of any cocatalysts and reductant.…”

Section: Introductionmentioning

confidence: 99%

Catalysis of metalloporphyrins for selective hydroxylation of phenol by H₂O₂

Zeng

Jiang

Zhu

et al. 2006

J. Porphyrins Phthalocyanines

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Liquid phase catalytic selective hydroxylation of phenol to catechol and hydroquinone was carried out in the presence of metalloporphyrins using hydrogen peroxide as oxidant and water as solvent. Five kinds of metal tetra(p-chlorophenyl)porphrin (T(p-Cl)PPMCl, M = Fe, Co, Mn, Cu, Zn) were studied. It was found that T(p-Cl)PPFeCl had high catalytic activity and diphenol selectivity for the hydroxylation of phenol to catechol and hydroquinone. The influence of various reaction parameters, namely, reaction temperature, solvent, ratio of substrate and oxidant, substrate concentration, the amount of catalyst, reaction time and pH value were investigated systematically. When water was used as solvent (10 mL), the optimum conditions were following: pH = 7, the concentration of phenol was 0.3 g/mL, the molar ratio of phenol and H 2 O 2 was 1/2, the molar ratio of catalyst and phenol was 7/100000, the reaction temperature was 65 °C and the reaction time was 1.5 h. Under above optimum conditions, the phenol conversion was up to 55.1%, and the selectivity of diphenol was almost up to 99.9%, the molar turnover numbers of the catalyst was about 7500. A possible mechanism was also proposed.

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Section: Introductionmentioning

confidence: 99%

Catalysis of metalloporphyrins for selective hydroxylation of phenol by H₂O₂

Zeng

Jiang

Zhu

et al. 2006

J. Porphyrins Phthalocyanines

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“…Transition metal complexes (TMCs) or metal oxides are typically used as such catalysts. , In contrast, the application of nontransition metal complexes (those of alkaline earth metals, Al, Ga, In, Tl, Sn, Pb, and Bi) in these reactions is much rarer. Most of the publications concern heterogeneous catalysis in which non-TMCs are used as supports or as catalysts themselves. − Examples of homogeneous oxidations of alkanes or olefins with peroxides catalyzed by non-TMCs include the hydroperoxidation of simple alkanes bearing nonactivated C–H bonds in the presence of [Al(H 2 O) 6 ] 3+ , [Be(H 2 O) 4 ] 2+ , and [M(H 2 O) 6 ] 3+ (M = Zn, Cd) and epoxidation of olefins with [Al(H 2 O) 6 ] 3+ , Sn(IV) (theoretical study), and Ga(III) (experimental and theoretical studies) species.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of Olefins with Hydrogen Peroxide Catalyzed by Bismuth Salts: A Mechanistic Study

et al. 2015

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Theoretical (DFT) calculations predict that soluble Bi salts exhibit catalytic activity toward oxidation of olefins with H2O2. Reaction occurs via two competitive channels: (i) nonradical epoxidation of the CC double bond and (ii) radical hydroperoxidation of the allylic C atom(s) with involvement of the HO• radicals, realized concurrently and leading to epoxide/diol and alkenylhydroperoxide products, respectively. The most plausible mechanism of epoxidation includes the substitution of a water ligand in the initial Bi aqua complex, hydrolysis of the coordinated H2O2, one-step oxygen transfer through a direct olefin attack at the unprotonated O atom of the OOH– ligand in [Bi(H2O)5(OOH)]2+, and liberation of the epoxide from the coordination sphere of Bi. The main conclusions of the theoretical calculations were confirmed by preliminary experiments on oxidation of cyclohexene, cyclooctene, and 1-octene with the systems Bi(NO3)3/H2O2/CH3CN + H2O and BiCl3/H2O2/CH3CN + H2O.

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