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Russian Chemical Bulletin

, Volume 59, Issue 5, pp 927–940 | Cite as

15-Hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis, structure, and complexation with the metal cations

  • A. I. Vedernikov
  • L. G. Kuz’mina
  • Yu. A. Strelenko
  • J. A. K. Howard
  • S. P. Gromov
Full Articles

Abstract

Novel 15-hydroxybenzomonothia-15-crown-5 containing the sulfur atom linked with the benzene ring and its S-oxide were synthesized. The stability constants for the complexes of the obtained benzocrown ethers and a reference 15-hydroxybenzo-15-crown-5 with Na, Ca, AgI, Cd, HgII, and PbII perchlorates were determined by 1H NMR titration. In MeCN-d3, the benzothiacrown ether demonstrates a high selectivity towards the thio- and oxothiophilic Hg2+ (logK 1 = 7.1) and Pb2+ ions (logK 1 = 7.4). In MeCN-d3-D2O mixtures, the stabilities of the most of complexes decrease sharply due to competitive hydration of the metal cations except for the “soft” Ag+ and Hg2+ ions having low affinity for the “hard” oxygen atoms and, on the contrary, very high affinity for the “soft” SII atoms. This results in the change in selectivity of complexation: at the water content in solution of 20%, the benzothiacrown ether binds preferably the Hg2+ (logK 1 = 5.0) and Ag+ ions (logK 1 = 2.7). In MeCN-d3, the benzothiacrown-derived sulfoxide is a weak and non-selective complexing agent towards all the metal cations under study; the reference 15-hydroxybenzo-15-crown-5 forms more stable complexes with the oxophilic sodium, calcium, and lead(ii) cations. The conformational features of the benzocrown ethers and their metal complexes established by NMR spectroscopy and X-ray diffraction are discussed. The found characteristics of the complexing ability of benzomonothia-15-crown-5 where the sulfur atom is in conjugation with the benzene ring reveal that the macrocyclic ligands with such a structure are promising as high-selective and efficient complexing agents for the “soft” mercury(ii) and silver(i) cations in acetonitrile-water mixtures.

Key words

benzothiacrown ethers synthesis structure complexes heavy metal cations stability constants NMR spectroscopy X-ray diffraction study 

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Copyright information

© Springer Science+Business Media, Inc.  2010

Authors and Affiliations

  • A. I. Vedernikov
    • 1
  • L. G. Kuz’mina
    • 2
  • 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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