An eco-friendly approach to the cyclohexane oxidation catalyzed by manganese porphyrins: Green and solvent-free systems

Guimarães, Adriano Silva; Schmitberger, Bernardo; Meireles, Alexandre Moreira; Martins, Dayse Carvalho da Silva; DeFreitas-Silva, Gilson

doi:10.1016/j.poly.2019.02.022

Cited by 9 publications

(16 citation statements)

References 35 publications

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“…The solvent effect in cyclohexane oxidation by PhI(OAC) 2 was reported by our group in a previous work. [8] Systems employing the third-generation catalysts 4 and 5 presented similar product total yields when compared to the first-generation analogs (1 and 2, Figure 5), although we verified an increase in the C-ol selectivity with isomers 4, 5, and 6. It was expected that the presence of bromine atoms at the β-pyrrole positions in the porphyrinic macrocycle should be responsible for destabilizing the high-valence active species [Mn(V)OP] (P = porphyrin) expected for this catalytic system and consequently, promoting an increase in the formation of oxygenated products.…”

Section: Cyclohexane Oxidation Reactionsmentioning

confidence: 59%

“…Several catalysts are studied for cyclohexane oxidation, [ 3–7 ] among which iron‐ and manganese‐porphyrins (FeP and MnP, respectively) can be highlighted. [ 8–11 ]…”

Section: Inroductionmentioning

confidence: 99%

“…Several catalysts are studied for cyclohexane oxidation, [3][4][5][6][7] among which iron-and manganese-porphyrins (FeP and MnP, respectively) can be highlighted. [8][9][10][11] Pioneering work in this area was developed by Groves et al, [12] who promoted the reaction using iodosylbenzene (PhIO) as an oxidant, dichloromethane as the solvent, and a FeP as the catalyst (mesotetraphenyliron(III) chloride, [Fe(TPP)Cl]). It affords moderate catalytic results (8% cyclohexanol) once the metalloporphyrin structure is easily destroyed under the oxidizing conditions of the catalytic reaction.…”

Section: Inroductionmentioning

confidence: 99%

“…In this way, the use of cocatalysts, such as imidazole or other nitrogenated bases, has been demonstrated in the literature to improve the efficiency of the oxidation reactions mediated by metalloporphyrins. [8,9,74,85] These species can interact with one of the free active sites of the metallic center, destabilizing the high-valence active species [Mn(V)OP] and favoring the oxygen atom transfer to the substrate. [85] In the same way, water can also be used as a cocatalyst, as described in the literature.…”

Section: Cyclohexane Oxidation Reactionsmentioning

confidence: 99%

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Exploring manganese pyridylporphyrin isomers for cyclohexane oxidation: First‐generation catalysts are better than third‐generation ones

Meireles

Guimarães

Querino

et al. 2021

Applied Organom Chemis

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Manganese porphyrins are widely studied as catalysts for oxidation reactions of different organic substrates. In this work, we evaluate the catalytic activity of manganese complexes derived from meso-tetrakis(2-, 3-, or 4-pyridyl) porphyrin isomers, [Mn(TXPyP)]Cl (X = 2, 3, or 4), and the respective β-octabrominated counter-parts, [Mn(Br 8 TXPyP)], for oxidation of cyclohexane by PhI(OAc) 2 . At first, we describe the synthesis and characterization of a new third-generation manganese porphyrin, [Mn(Br 8 T4PyP)]. It presented a more positive value of half-wave potential (À0.287 V vs. Fc + /Fc) and a lower solubility in organic solvents among the isomers. In general, the third-generation catalysts [Mn(Br 8 TXPyP)] showed lower catalytic activity than those of the first-generation [Mn(TXPyP)]Cl in all systems studied. In addition, the use of water or imidazole as cocatalysts did not increase the yield or selectivity of the systems. Finally, when evaluating the use of the classic oxidant PhIO, there was a decrease in yield for all systems, indicating that PhI(OAc) 2 is a good substitute for this oxidant in catalytic systems.

show abstract

Section: Cyclohexane Oxidation Reactionsmentioning

confidence: 59%

“…Several catalysts are studied for cyclohexane oxidation, [ 3–7 ] among which iron‐ and manganese‐porphyrins (FeP and MnP, respectively) can be highlighted. [ 8–11 ]…”

Section: Inroductionmentioning

confidence: 99%

Section: Inroductionmentioning

confidence: 99%

Section: Cyclohexane Oxidation Reactionsmentioning

confidence: 99%

See 2 more Smart Citations

Exploring manganese pyridylporphyrin isomers for cyclohexane oxidation: First‐generation catalysts are better than third‐generation ones

Meireles

Guimarães

Querino

et al. 2021

Applied Organom Chemis

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“…Metalloporphyrins have been widely used as impressive catalysts in broad chemical reactions [1][2][3][4][5][6][7], including hydroxylation [8,9], epoxidation [10,11], reduction of nitric oxide [12], oxidation of sulfides [13], radical reactions [14,15], halogenation [16], cycloaddition [17,18], and reduction [19,20]. During the application of metalloporphyrins, the characterization of reactive intermediates is of great importance for the understanding of reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Electronic Structural Properties of Catalytically Reactive Metalloporphyrin Intermediates

et al. 2020

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Metalloporphyrins have attracted great attention in the potential application of biomimetic catalysis. Especially, they were widely investigated as green catalysts in the chemical oxidation of various hydrocarbons through the catalytic activation of molecular oxygen. The structural properties of active central metal ions were reported to play a decisive role in catalytic activity. However, those delicate structural changes are difficult to be experimentally captured or elucidated in detail. Herein, we explored the electronic structural properties of metalloporphyrins (metal porphyrin (PMII, PMIIICl)) and their corresponding catalytically active intermediates (metal(III)-peroxo(PMIII-O2), metal(III)-hydroperoxo(PMIII-OH), and metal(IV)-oxo(PMIV=O), (M=Fe, Mn, and Co)) through the density functional theory method. The ground states of these intermediates were determined based on the assessment of relative energy and the corresponding geometric structures of ground states also further confirmed the stability of energy. Furthermore, our analyses of Mulliken charges and frontier molecular orbitals revealed the potential catalytic behavior of reactive metalloporphyrin intermediates.

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Norfloxacin and gentamicin degradation catalyzed by manganese porphyrins under mild conditions: the importance of toxicity assessment

Santos

Lebron

Moreira

et al. 2021

Environ Sci Pollut Res

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An eco-friendly approach to the cyclohexane oxidation catalyzed by manganese porphyrins: Green and solvent-free systems

Cited by 9 publications

References 35 publications

Exploring manganese pyridylporphyrin isomers for cyclohexane oxidation: First‐generation catalysts are better than third‐generation ones

Exploring manganese pyridylporphyrin isomers for cyclohexane oxidation: First‐generation catalysts are better than third‐generation ones

Theoretical Study on Electronic Structural Properties of Catalytically Reactive Metalloporphyrin Intermediates

Norfloxacin and gentamicin degradation catalyzed by manganese porphyrins under mild conditions: the importance of toxicity assessment

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