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Russian Chemical Bulletin

, Volume 59, Issue 6, pp 1192–1206 | Cite as

Nitro derivatives of N-alkylbenzoaza-15-crown-5: synthesis, structures, and complexation with metal and ammonium cations

  • S. N. Dmitrieva
  • M. V. Churakova
  • N. A. Kurchavov
  • A. I. Vedernikov
  • L. G. Kuz’mina
  • A. Ya. Freidzon
  • A. A. Bagatur’yants
  • Yu. A. Strelenko
  • J. A. K. Howard
  • S. P. Gromov
Full Articles

Abstract

A number of N-alkylnitrobenzoaza-15-crown-5 with the macrocycle N atom conjugated with the benzene ring were obtained. The structural and complexing properties of these compounds were compared with those of model nitrobenzo- and N-(4-nitrophenyl)aza-15-crown-5 using X-ray diffraction, 1H NMR spectroscopy, and DFT calculations. The macrocyclic N atom of benzoazacrown ethers are characterized by a considerable contribution of the sp3-hybridized state and a pronounced pyramidal geometry; the crownlike conformation of the macrocycle is preorganized for cation binding, which facilitates complexation. The stability constants of the complexes of crown ethers with the NH4 +, EtNH3 +, Na+, K+, Ca2+, and Ba2+ ions were determined by 1H NMR titration in MeCN-d3. The most stable complexes were obtained with alkaline-earth metal cations, which is due to the higher charge density at these cations. The characteristics of the complexing ability of N-alkylnitrobenzoaza-15-crown-5 toward alkaline earth metal cations are comparable with analogous characteristics of nitrobenzo-15-crown-5 and are much better than those of N-(4-nitrophenyl)aza-15-crown-5.

Key words

benzoazacrown ethers synthesis structures complexation metal cations ammonium ions stability constants X-ray diffraction analysis 1H NMR spectroscopy quantum chemical calculations density functional theory 

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Copyright information

© Springer Science+Business Media, Inc.  2010

Authors and Affiliations

  • S. N. Dmitrieva
    • 1
  • M. V. Churakova
    • 1
  • N. A. Kurchavov
    • 1
  • A. I. Vedernikov
    • 1
  • L. G. Kuz’mina
    • 2
  • A. Ya. Freidzon
    • 1
  • A. A. Bagatur’yants
    • 1
  • Yu. A. Strelenko
    • 3
  • J. A. K. Howard
    • 4
  • S. P. Gromov
    • 1
  1. 1.Photochemistry CenterRussian Academy of SciencesMoscowRussian Federation
  2. 2.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation
  3. 3.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation
  4. 4.Department of ChemistryUniversity of DurhamDurhamUK

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