Publications by authors named "Iulius Markovits"

The electrochemical performance of ionic liquid electrolytes containing different sodium salts dissolved in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) evaluated in a half-cell configuration using spherical P2-NaCoMnO (NCO) cathodes are reported. Among the various electrolytes investigated, sodium bis(fluorosulfonyl)imide (NaFSI) (0.5 M) in BMPTFSI shows the best electrochemical performance with a significant improvement in cycling stability (90% capacity retention after 500 cycles at 50 mA g in a half cell versus Na metal anode) compared with conventional NaClO (1 M) in ethylene carbonate/propylene carbonate electrolytes (39% retention after 500 cycles).

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Article Synopsis
  • Hydrophobic imidazolium-based ionic liquids (ILs) are effective catalysts for epoxidizing unfunctionalized olefins in water using hydrogen peroxide as the oxidant.
  • The ILs, though initially insoluble in the substrate and water, dissolve well in aqueous H2 O2 due to a unique interaction with perrhenate.
  • These catalysts not only facilitate the reaction but also enhance the solubility of hydrophobic substrates in water, making them easily recyclable after the reaction is complete.
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A series of imidazolium perrhenates with different substituents at the imidazolium ring were synthesised and characterised, including single crystal X-ray diffraction. The effect of the substitution pattern on the state of aggregation of the compounds, the charge delocalisation and the ion pairing interaction via hydrogen bonds was studied. Particularly the substitution at the C2 position of the imidazolium ring was shown to be crucial to fine-tune the ion contacts.

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Organic-phase supramolecular ion pair (SIP) host-guest assemblies of perrhenate anions (ReO4(-)) with ammonium amide receptor cations are reported. These compounds act as catalysts for the epoxidation of alkenes by aqueous hydrogen peroxide under biphasic conditions and can be recycled several times with no loss in activity.

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The combination of pentaerythritol with nucleophilic halide salts such as nBu4NI is used as a dual catalyst system for the cycloaddition of carbon dioxide (CO2) with a broad range of organic epoxides yielding the respective cyclic carbonates. Due to synergistic effects of the organocatalysts, excellent yields and selectivities could be achieved under mild reaction conditions. Moreover, the nontoxic, cost-efficient, and readily available system is easily recyclable without significant loss of reactivity, representing an exceptional sustainable approach for the fixation of CO2.

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Methyldioxorhenium (MDO)-catalyzed C-O bond cleavage of a variety of lignin β-O-4-model compounds yields phenolic and aldehydic compounds in homogeneous phase under mild reaction conditions. MDO is in situ generated by reduction of methyltrioxorhenium (MTO) and is remarkably stable under the applied reaction conditions allowing its reuse for least five times without significant activity loss. Based on the observed and isolated intermediates, 17 O- and 2 H-isotope labeling experiments, DFT calculations, and several spectroscopic studies, a reaction mechanism is proposed.

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Article Synopsis
  • Imidazolium-based ionic liquids with perrhenate anions are highly effective for the epoxidation of olefins using H2O2, producing nearly perfect yields of cyclooctene.
  • The reaction mechanism differs from traditional methods, as it involves hydrogen bonds that activate the oxidant, rather than forming peroxo complexes.
  • The study highlights the role of the ionic liquid environment and examined various oxidants, demonstrating good yields of epoxides from different olefinic substrates.
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