Epoxidations catalyzed by an ionic manganese(III) porphyrin and characterization of manganese(V, IV)-oxo porphyrin complexes by UV–vis spectrophotometer in ionic liquid solution

Zhang, Hong-Jiao; Liu, Ye; Lu, Yong; He, Xin; Wang, Xia; Ding, Xia

doi:10.1016/j.molcata.2008.03.001

Cited by 23 publications

(11 citation statements)

References 35 publications

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“…As a model compound of Cytochrome P450 enzyme, metalloporphyrin has been widely used in C–H activation and oxidation reactions. − Much effort was exerted to expand the metalloporphyrin family, especially in the field of water-soluble porphyrin − and porphyrin catalysts with higher selectivity or reactivity. − …”

Section: Introductionmentioning

confidence: 99%

“…Catalyst recycling and the aqueous catalysis process are required to develop water-soluble porphyrins. − Recycling metalloporphyrins is one of the most important steps for the large-scale practical application of the related catalytic process due to the high cost of this catalyst. However, recycling traditional metalloporphyrins (such as meso -tetraphenylporphyrin iron and its analogue) is difficult because their solubility in water is quite poor.…”

Section: Introductionmentioning

confidence: 99%

“…However, recycling traditional metalloporphyrins (such as meso -tetraphenylporphyrin iron and its analogue) is difficult because their solubility in water is quite poor. Modifying metalloporphyrins using a functional group including a cation–anion pair can make this catalyst soluble in water. − The solubility properties of these modified catalysts change with the difference of the cations and anions, which makes the phase separation from less polar organic solvents and aqueous media possible. Another purpose in developing a water-soluble porphyrin is aqueous catalysis.…”

Section: Introductionmentioning

confidence: 99%

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Structure–Reactivity Relationships of Metalloporphyrin Modified by Ionic Liquid and Its Analogue

Liu

et al. 2011

J. Phys. Chem. C

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The influence of ionic liquid (IL) modification on the reactivity of metalloporphyrins was carefully investigated to design a recoverable and highly effective metalloporphyrin catalyst. On the basis of the research, which included a total of 34 different catalysts, the following modification methods make metalloporphyrins more powerful: (1) increasing the spin density (SDO), charge (QO), or isotropic fermi contact couplings (IFCCO) of the O atom in the FeO part and (2) decreasing the spin density carried by the Fe atom (SDFe) or the HOMO–LUMO gap between a catalyst and reactant (LUMOC–HOMOR). The order of the correlation between the structure parameters and the reactivity is SDo > Qo > IFCCO ≈ SDFe ≈ LUMOC–HOMOR. Compared with changing the cation of metalloporphyrins, changing the anion is a more effective way to increase the reactivity. The order is AlBr4 – > AlCl4 – > BCl4 – > PF6 – > AsF6 – > SbF6 – > BF4 – > Tf2N– > AlF4 – > HSO4 – > CF3SO3 – > CF3CO2 – > Cl–. However, the long distance between the IL part and the catalytic active center or electron-donating substituent on the N atom weaken the influence induced by the IL modification. These structure–reactivity relationships could be used in designing a catalyst.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure–Reactivity Relationships of Metalloporphyrin Modified by Ionic Liquid and Its Analogue

Liu

et al. 2011

J. Phys. Chem. C

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“…1,2 This tunability can be further expanded by introducing binary or ternary IL mixtures, for which the number of available ILs is innumerable. Binary ILs have been applied to solar cells, [3][4][5][6][7][8][9][10][11][12][13][14] gaschromatography, 15 organicreactions, 16 inorganicreactions, [17][18][19][20] and enzymatic reactions. 21,22 When an IL consists of hydrophobic cations and anions, the IL is immiscible with water (W) and forms an IL-W two-phase system.…”

Section: Introductionmentioning

confidence: 99%

Determination of the Activity of 1-Methyl-3-octylimidazolium Bis(trifluoromethanesulfonyl)amide in Binary Ionic Liquids from the Solubility in Water

2010

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For the binary ionic liquid (IL)-water (W) two-phase systems formed by the ILs 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)amide ([C 8 mim + ][C 1 C 1 N -]) and tetrahexylammonium bis(trifluoromethanesulfonyl)amide, which have a common anion, the activities of [C 8 mim + ][C 1 C 1 N -] in the water-saturated binary IL phase have been determined from the solubility of C 8 mim + in the W phase at different mole fractions of the IL (x C 8 mimC 1 C 1 N IL ) at five different temperatures between (278 and 328) K. The variation of the activity coefficients of [C 8 mim + ][C 1 C 1 N -] in the IL phase with x C 8 mimC 1 C 1 N IL is by and large in harmony with the regular solution model. However, small but systematic deviations from the model have been discerned and are likely to result from the phase transition of the binary ILs at x C 8 mimC 1 C 1 N IL ≈ 0.3, which causes changes in the microheterogeneity in the assemblies of the IL-constituent ions. The standard Gibbs energy for transfer of [C 8 mim + ][C 1 C 1 N -] from the water-saturated IL to W (∆ tr G m,C 8 mimC 1 C 1 N Q,ILfW ), which was evaluated from the temperature dependence of the solubility, is 30-34 kJ · mol -1 over the temperature range studied. The standard enthalpy for transfer of [C 8 mim + ][C 1 C 1 N -] from IL to W is positive and increases linearly from 4 kJ · mol -1 at 283 K to 24 kJ · mol -1 at 318 K.

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“…In heme enzymes, the high‐valent oxo‐iron porphyrins are considered as versatile catalysts in the substrate hydroxylation and epoxidation reactions [4–8] . Besides, many synthetic methods have been developed to prepare oxo‐manganese porphyrins, [9–16] due to manganese having many available oxidation states and coordination numbers. The high‐valent oxo‐manganese species have great potential redox activity – [17–19a] .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Selectivity of Norcarane Oxidation by Oxo‐Manganese(V) Porphyrin Complexes

Hada

Nakatani

2022

ChemPhysChem

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Oxo‐Mn(V) porphyrin complexes perform competitive hydroxylation, desaturation, and radical rearrangement reactions using diagnostic substrate norcarane. Initial C−H cleavage proceeds through the two hydrogen abstraction steps from the two adjacent carbon on the norcarane and then through selective reactions various products are generated. Using density functional theory calculations, we show that the hydroxylation and desaturation reactions are triggered by a rate‐determining H‐abstraction step, whereas the rate‐determining step for the radical rearrangement is located at the rebound step (TS2). We find that the endo‐2 reaction is favorable over other reactions, which is consistent with the experimental result. Furthermore, the competitive pathways for norcarane oxidation depend on the non‐covalent interaction between norcarane and the porphyrin‐ring, and orbital energy gaps between donor and acceptor orbitals because of stable or unstable acceptor orbital. The stereo‐ and regio‐selectivities of norcarane oxidation are hardly sensitive to the zero‐point energy and thermal free energy corrections.

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Epoxidations catalyzed by an ionic manganese(III) porphyrin and characterization of manganese(V, IV)-oxo porphyrin complexes by UV–vis spectrophotometer in ionic liquid solution

Cited by 23 publications

References 35 publications

Structure–Reactivity Relationships of Metalloporphyrin Modified by Ionic Liquid and Its Analogue

Structure–Reactivity Relationships of Metalloporphyrin Modified by Ionic Liquid and Its Analogue

Determination of the Activity of 1-Methyl-3-octylimidazolium Bis(trifluoromethanesulfonyl)amide in Binary Ionic Liquids from the Solubility in Water

Mechanistic Insights into the Selectivity of Norcarane Oxidation by Oxo‐Manganese(V) Porphyrin Complexes

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