Halogenated meso-phenyl Mn(III) porphyrins as highly efficient catalysts for the synthesis of polycarbonates and cyclic carbonates using carbon dioxide and epoxides

Cuesta-Aluja, Laia; Castilla, Javier; Masdeu‐Bultó, Anna M.; Henriques, César A.; Calvete, Mário J. F.; Pereira, Mariette M.

doi:10.1016/j.molcata.2015.10.025

Cited by 39 publications

(21 citation statements)

References 49 publications

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“…The reactions were performed in the absence of solvent, under previously optimised conditions (50 bar CO2, 80 °C), using a 0.07 mol % catalyst [37], with and without bis(triphenylphosphine)iminium chloride (PPNCl) as a co-catalyst. The results are presented in Table 1.…”

Section: Effect Of the Metalmentioning

confidence: 99%

“…Recently, we reported the application of meso-phenyl Mn(III) porphyrins as highly efficient catalysts for coupling the reactions of epoxides with CO2, showing that the introduction of electron withdrawing halogen atoms in the ortho positions of meso-tetraphenylporphyrin manganese(III) complexes strengthens the Lewis acidity of the metal centre, thereby increasing their catalytic activity [37]. Earlier, in 2000, Holmes reported the use of tetrakis(pentafluorophenyl)porphyrinato chromium(III) chloride (6) in the copolymerisation reaction of cyclohexene oxide with CO2 under supercritical conditions [20].…”

Section: Introductionmentioning

confidence: 99%

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Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

et al. 2017

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Metal complexes of meso-arylporphyrins (Cr(III), Fe(III), and Zn(II)) were evaluated in the coupling reaction of cyclohexene oxide (CHO) with CO 2 in compressed medium, where the Cr complexes were demonstrated to be the most active systems, leading predominantly to copolymerisation products. It is noteworthy that no addition of solvent was required. To improve the catalytic activity, and to simultaneously increase the solubility in compressed CO 2 , a new fluorinated catalyst, tetrakis(4-trifluoromethylphenyl)porphyrinatochromium(III) chloride (CrCl-pCF 3 TPP), was applied to this reaction. The alternating copolymerisation of CHO with CO 2 , using the Cr(III) fluorinated porphyrin catalyst, required the use of a co-catalyst, bis(triphenylphosphine)iminium chloride (PPNCl), with the best yields of copolymers being obtained at 80 • C, and CO 2 pressures in the range of 50-110 bar, over a period of 24 h, with a low catalyst/substrate molar ratio (0.07%). The polycarbonate's structure was analysed by 1 H NMR, 13 C NMR, and MALDI-TOF spectroscopy, which demonstrated high carbonate incorporations (98-99%). Gel permeation chromatography revealed number-average molecular weights (M n ) in the range of 4800-12,800 and narrow molecular weight distributions (M w /M n ≤ 1.63).

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Section: Effect Of the Metalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

et al. 2017

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“…Among these systems, heterocyclic macrocycle metal complexes, such as metalloporphyrins and metallocorroles, are promising catalysts due to the possibility of altering electronic and steric characteristics by modifications of their framework . Also, in square pyramidal metalloporphyrins the axial counterion may influence the stability and catalytic activity and additionally can be readily replaced …”

Section: Introductionmentioning

confidence: 99%

Mn^III Porphyrins: Catalytic Coupling of Epoxides with CO₂ under Mild Conditions and Mechanistic Considerations

et al. 2019

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A series of 5,10,15,20‐tetrakis(2,3‐dichlorophenyl)porphyrinate complexes of manganese(III) [MnIII(T2,3DCPP)X] with six different axial ligands (X=NO3−, AcO−, IO3−, Br−, Cl−, HO−) were investigated as catalysts in the cycloaddition reactions of CO2 and styrene oxide (SO), under mild conditions, i. e., atmospheric pressure and 60 °C. [MnIIIT(2,3DCPP)IO3] showed the best catalytic performance, selectively producing the respective cyclic carbonate from diverse epoxides using tetrabutylammonium bromide as a nucleophile source. Mechanistic considerations were inferred from electronic spectra and spectrophotometric titrations, showing that there are a series of equilibriums involved in the formation of the catalytic active species. Stability constants for the proposed equilibrium models were determined using SQUAD software. A catalytic cycle has been proposed based on those observations.

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“…[65][66][67][68][69][70] Therefore,m ore robustc atalysts such as heterogeneous and/orb iphasic systems have been lately developed,n amely those based on metal oxides, [71,72] supported gold catalysts, [73][74][75] sodium phosphotungstate, [76] and ionic liquids, [77] most of them using alkyl hydroperoxides as oxygen donors. [82] Particularly,f luorinated groups are highly advantageous because they also increase the catalyst's solubility in compressed CO 2 ,a voiding the use of solvents. [82] Particularly,f luorinated groups are highly advantageous because they also increase the catalyst's solubility in compressed CO 2 ,a voiding the use of solvents.…”

Section: Introductionmentioning

confidence: 99%

Hybrid Metalloporphyrin Magnetic Nanoparticles as Catalysts for Sequential Transformation of Alkenes and CO₂ into Cyclic Carbonates

et al. 2018

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The synthesis and full characterization of manganese and chromium metalloporphyrins and hybrid magnetic nanocomposites prepared thereof is described. Their application in homogeneous and heterogeneous sequential epoxidation/CO2 cycloaddition reactions by using O2 or H2O2 as the oxidant showed high activity and selectivity for the preparation of a variety of cyclic carbonates directly from olefins. The combination of manganese and chromium nanocomposites allowed us to set the keystone for the development of a reusable dual catalytic system to transform olefins into cyclic carbonates.

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Halogenated meso-phenyl Mn(III) porphyrins as highly efficient catalysts for the synthesis of polycarbonates and cyclic carbonates using carbon dioxide and epoxides

Cited by 39 publications

References 49 publications

Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

Mn^III Porphyrins: Catalytic Coupling of Epoxides with CO₂ under Mild Conditions and Mechanistic Considerations

Hybrid Metalloporphyrin Magnetic Nanoparticles as Catalysts for Sequential Transformation of Alkenes and CO₂ into Cyclic Carbonates

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Halogenated meso-phenyl Mn(III) porphyrins as highly efficient catalysts for the synthesis of polycarbonates and cyclic carbonates using carbon dioxide and epoxides

Cited by 39 publications

References 49 publications

Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins

MnIII Porphyrins: Catalytic Coupling of Epoxides with CO2 under Mild Conditions and Mechanistic Considerations

Hybrid Metalloporphyrin Magnetic Nanoparticles as Catalysts for Sequential Transformation of Alkenes and CO2 into Cyclic Carbonates

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Product

Resources

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Mn^III Porphyrins: Catalytic Coupling of Epoxides with CO₂ under Mild Conditions and Mechanistic Considerations

Hybrid Metalloporphyrin Magnetic Nanoparticles as Catalysts for Sequential Transformation of Alkenes and CO₂ into Cyclic Carbonates