Biomimetic kinetics and mechanism of cyclohexene epoxidation catalyzed by metalloporphyrins

Zhou, Xiantai; Ji, Hongbing

doi:10.1016/j.cej.2009.10.066

Cited by 68 publications

(51 citation statements)

References 46 publications

(52 reference statements)

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“…[12][13][14][15][16][17][18][19][20] The modification of phenyl groups with electron-withdrawing or bulky substituents has been found to enhance MeP catalytic activity by creating a cage around the metal-oxo, thus avoiding catalyst self-degradation or formation of inactive µ-oxo dimers. 29,30 Bearing these advantages in mind, this metalloporphyrin was selected for binding onto magnetic amino-substituted nanoparticles.…”

Section: Resultsmentioning

confidence: 99%

“…10,11 Many MeP-based catalytic systems have been investigated for the oxidation of various substrates, especially alkene epoxidation and alkane hydroxylation. [12][13][14][15][16] The best catalytic systems have also been utilized in the oxidation of drugs, herbicides and other substrates, with good efficiencies. [17][18][19][20] The design and refinement of these bioinspired catalytic systems have progressed with the synthesis of MePs with increasing number of substituents in the porphyrin ring 21 and the use of various oxidants.…”

Section: Introductionmentioning

confidence: 99%

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Iron(III) porphyrin covalently supported onto magnetic amino-functionalized nanospheres as catalyst for hydrocarbon and herbicide oxidations

Santos¹,

Faria²,

Amorin³

et al. 2012

J. Braz. Chem. Soc.

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Este trabalho descreve a imobilização por ligação covalente de uma ferroporfirina, cloreto de 5,10,15,20-tetraquis(pentafluorofenil)porfirinaferro(III) (FeTFPP), sobre nanoesferas de maguemita cobertas com sílica aminofuncionalizada. O material resultante (nomeado γ-Fe 2 O 3 /SiO 2 -NHFeP) foi caracterizado por espectroscopia no infravermelho por refletância difusa (DRIFTS) e espectroscopia de absorção UV-Vis. A atividade catalítica desta ferroporfirina magnética foi investigada em reações de oxidação de hidrocarbonetos (estireno, (Z)-cicloocteno e R-(+)-limoneno) e de um herbicida (simazina), utilizando-se peróxido de hidrogênio ou ácido metacloroperbenzóico. Os produtos das reações de oxidação de hidrocarbonetos e simazina foram analisados por cromatografia em fase gasosa (GC) e cromatografia líquida de alta resolução (HPLC), respectivamente. Este sistema catalítico provou ser eficiente e seletivo na oxidação dos hidrocarbonetos, levando a altos rendimentos na oxidação do estireno (89%), cicloocteno (71%) e (+)-limoneno (86%). Na oxidação da simazina catalisada pelo γ-Fe 2 O 3 /SiO 2 -NHFeP, obteve-se 100% de seletividade para um produto desalogenado (OEAT), enquanto a mesma reação em meio homogêneo levou à formação de diversos produtos de oxidação. O catalisador pode ser facilmente recuperado pela aplicação de um campo magnético externo e lavado ao final das reações. Nos estudos de reutilização do catalisador para a oxidação do (+)-limoneno, a atividade catalítica foi mantida em 90%, mesmo após 10 reações consecutivas. This work describes the covalent immobilization of an ironporphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron(III) chloride (FeTFPP), onto maghemite/silica magnetic nanospheres covered with aminofunctionalized silica. The resulting material (γ-Fe 2 O 3 /SiO 2 -NHFeP) was characterized by diffuse reflectance infrared spectroscopy (DRIFTS) and UV-Vis absorption spectroscopy. The catalytic activity of this magnetic ironporphyrin was investigated in the oxidation of hydrocarbons (styrene, (Z)-cyclooctene and R-(+)-limonene) and an herbicide (simazine) by hydrogen peroxide or 3-chloroperoxybenzoic acid. Hydrocarbon and simazine oxidation reaction products were analyzed by gas chromatography (GC) and high performance liquid chromatography (HPLC), respectively. This catalytic system proved to be efficient and selective for hydrocarbon oxidation, leading to high product yields from styrene (89%), cyclooctene (71%) and R-(+)-limonene (86%). Simazine oxidation was attained with 100% selectivity for a dechlorinated product (OEAT), while several oxidation products were obtained for the same catalyst in homogeneous media. The catalyst can be easily recovered through application of an external magnetic field and washed after reaction. Catalyst reuse experiments for R-(+)-limonene oxidation have shown that the catalytic activity is kept at 90% after 10 consecutive reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Iron(III) porphyrin covalently supported onto magnetic amino-functionalized nanospheres as catalyst for hydrocarbon and herbicide oxidations

Santos¹,

Faria²,

Amorin³

et al. 2012

J. Braz. Chem. Soc.

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“…It was reported that aerobic epoxidation of olefins in solution can be efficiently achieved under quite mild conditions over some transition metal complexes by using molecular oxygen as oxidant and aliphatic aldehyde as co-reactant, which is the so-called "Mukaiyama" procedure [8][9][10][11][12][13]. Although the usage of co-reactant aldehyde is undesirable, the Mukaiyama method is still worthy of studying for its great advantages, such as very mild operation conditions (low temperatures, atmospheric pressure), high epoxide selectivity, low cost and environmental-friendly nature of the oxidant [11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Epoxidation of olefins with oxygen/isobutyraldehyde over transition-metal-substituted phosphomolybdic acid on SBA-15

Song

Zhu

et al. 2016

Catalysis Today

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“…[73][74][75][76] Iron, ruthenium and cobalt also showed excellent activity for cyclohexene epoxidation by molecular oxygen (Table 3). [77] Comparing the catalytic activities of different porphyrin catalysts, it was found that manganese porphyrin was the most effective since cyclohexene could be completely converted within 4.0 hours. The catalytic activity of different metalloporphyrins is probably influenced by their electric potential and the stability of different valences of metal atoms.…”

Section: Aldehydes As Reductantmentioning

confidence: 99%

Biomimetic Epoxidation of Olefins Catalyzed by Metalloporphyrins with Molecular Oxygen

Ji¹,

Zhou²

2011

Biomimetic Based Applications

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Biomimetic kinetics and mechanism of cyclohexene epoxidation catalyzed by metalloporphyrins

Cited by 68 publications

References 46 publications

Iron(III) porphyrin covalently supported onto magnetic amino-functionalized nanospheres as catalyst for hydrocarbon and herbicide oxidations

Iron(III) porphyrin covalently supported onto magnetic amino-functionalized nanospheres as catalyst for hydrocarbon and herbicide oxidations

Epoxidation of olefins with oxygen/isobutyraldehyde over transition-metal-substituted phosphomolybdic acid on SBA-15

Biomimetic Epoxidation of Olefins Catalyzed by Metalloporphyrins with Molecular Oxygen

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