Activation of hydrogen peroxide by ionic liquids: Mechanistic studies and application in the epoxidation of olefins

Iulius I E Markovits, Wilhelm A. Eger, Shuang Yue, Mirza Cokoja, Christian J. Münchmeyer, Bo Zhang, Ming Dong Zhou, Alexander Genest, J. Mink, Shu Liang Zang, Notker Rösch, Fritz E. Kühn

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Imidazolium-based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H2O 2 as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long-known molecular transition-metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H2O2, urea hydrogen peroxide, and tert-butyl hydrogen peroxide) on the efficiency of the epoxidation of cis-cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex.

Original languageEnglish
Pages (from-to)5972-5979
Number of pages8
JournalChemistry - A European Journal
Volume19
Issue number19
DOIs
Publication statusPublished - May 3 2013

Fingerprint

Ionic Liquids
Epoxidation
Alkenes
Oxidants
Ionic liquids
Hydrogen peroxide
Hydrogen Peroxide
Olefins
Chemical activation
Epoxy Compounds
Discrete Fourier transforms
Urea
Nuclear magnetic resonance spectroscopy
Transition metals
Anions
Raman spectroscopy
Cations
Hydrogen bonds
Negative ions
Salts

Keywords

  • density functional calculations
  • epoxidation
  • ionic liquids
  • peroxides
  • rhenium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Markovits, I. I. E., Eger, W. A., Yue, S., Cokoja, M., Münchmeyer, C. J., Zhang, B., ... Kühn, F. E. (2013). Activation of hydrogen peroxide by ionic liquids: Mechanistic studies and application in the epoxidation of olefins. Chemistry - A European Journal, 19(19), 5972-5979. https://doi.org/10.1002/chem.201203208

Activation of hydrogen peroxide by ionic liquids : Mechanistic studies and application in the epoxidation of olefins. / Markovits, Iulius I E; Eger, Wilhelm A.; Yue, Shuang; Cokoja, Mirza; Münchmeyer, Christian J.; Zhang, Bo; Zhou, Ming Dong; Genest, Alexander; Mink, J.; Zang, Shu Liang; Rösch, Notker; Kühn, Fritz E.

In: Chemistry - A European Journal, Vol. 19, No. 19, 03.05.2013, p. 5972-5979.

Research output: Contribution to journalArticle

Markovits, IIE, Eger, WA, Yue, S, Cokoja, M, Münchmeyer, CJ, Zhang, B, Zhou, MD, Genest, A, Mink, J, Zang, SL, Rösch, N & Kühn, FE 2013, 'Activation of hydrogen peroxide by ionic liquids: Mechanistic studies and application in the epoxidation of olefins', Chemistry - A European Journal, vol. 19, no. 19, pp. 5972-5979. https://doi.org/10.1002/chem.201203208
Markovits, Iulius I E ; Eger, Wilhelm A. ; Yue, Shuang ; Cokoja, Mirza ; Münchmeyer, Christian J. ; Zhang, Bo ; Zhou, Ming Dong ; Genest, Alexander ; Mink, J. ; Zang, Shu Liang ; Rösch, Notker ; Kühn, Fritz E. / Activation of hydrogen peroxide by ionic liquids : Mechanistic studies and application in the epoxidation of olefins. In: Chemistry - A European Journal. 2013 ; Vol. 19, No. 19. pp. 5972-5979.
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