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Russian Chemical Bulletin

, Volume 54, Issue 3, pp 623–632 | Cite as

Synthesis of 1,3-bis(acetylacetonyloxy)- and 1,3-bis(benzoylacetonyloxy)benzene and their complexation with lanthanide ions

  • S. N. Podyachev
  • I. A. Litvinov
  • A. R. Mustafina
  • R. R. Shagidullin
  • W. D. Habicher
  • A. I. Konovalov
Article

Abstract

Claisen condensation of 1,3-bis(methoxycarbonylmethoxy)benzene with acetone and acetophenone afforded new chelating ligands consisting of two β-diketonate fragments, viz., 1,3-bis(acetylacetonyloxy)benzene and 1,3-bis(benzoylacetonyloxy)benzene, which are linked to each other through the resorcinol spacer. In the crystal, 1,3-bis(acetylacetonyloxy)benzene, unlike the starting ester, adopts a planar conformation and exists in the enol form. The acidities of these compounds and their complexation with lanthanide ions in aqueous ethanolic solutions were studied by pH-potentiometry. Depending on the concentration conditions and pH, the La3+, Gd3+, and Lu3+ ions form 1 : 1, 1 : 2, or 1 : 3 complexes with bis(β-diketones). The stability of the complexes increases as the atomic number of the lanthanide increases (La3+ < Gd3+ ≤ Lu3+). The complexation constants and selectivity of complexation substantially increase with increasing degree of deprotonation of the ligands, which indicates that both chelate groups of the ligands are simultaneously involved in coordination. The Ph substituents in bis(β-diketone) have a considerable effect on the composition and stability of complexes with lanthanide ions due to additional noncovalent inner-sphere interactions.

Key words

β-diketone X-ray diffraction analysis pH potentiometry complexation lanthanides stability constants 1,3-bis(acetylacetonyloxy)benzene 1,3-bis(benzoylacetonyloxy)benzene 

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Copyright information

© Springer Science+Business Media, Inc. 2005

Authors and Affiliations

  • S. N. Podyachev
    • 1
  • I. A. Litvinov
    • 1
  • A. R. Mustafina
    • 1
  • R. R. Shagidullin
    • 1
  • W. D. Habicher
    • 2
  • A. I. Konovalov
    • 1
  1. 1.A. E. Arbuzov Institute of Organic and Physical ChemistryKazan Research Center of the Russian Academy of SciencesKazanRussian Federation
  2. 2.Dresden University of TechnologyInstitute of Organic ChemistryDresdenGermany

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