Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Conductometric Behavior of Univalent Cation-Podand Complexes in Methanol

  • Kim, Dae-Yeon (Department of Chemistry, Gyeongsang National University) ;
  • Jung, Jong-Hwa (Department of Chemistry, Gyeongsang National University) ;
  • Chun, Jae-Sang (Korea Research Institute of Chemical Technology) ;
  • Lee, Shim-Sung (Department of Chemistry, Gyeongsang National University)
  • Published : 1994.11.20
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Abstract

The stability constants, log K of the 1 : 1 complexation for IA ions, $Ag^+$, and $Tl^+$ with a series of podands having different aromatic end-groups (I-IV) have been determined conductometrically in methanol at 25.0 $^{\circ}$C. Exceptionally the equivalent conductivity, ${\lambda}_{eq}\;of\;Li^+\;and\;Na^+$ were increased by the addition of I, because the complexed ions are less mobile than solvated ions. The order of log K values for I was $Ag^+{\gg}Tl^+>K^+>Na^+>Rb^+>Cs6+>Li^+$. The log K sequence of the podands for the certain cations was I>II>III${\geq}$IV. And every podands except IV showed the maximum selectivity for $Ag^+$ among the cations. These results were discussed in terms of the aromatic end-group effects, such as hetero-donor atoms or conformational changes by ${\pi}-{\pi}$ stacking interactions. The detailed conformations of ${\pi}-{\pi}$ stacking were also discussed by the observations of upfield shifts of some aromatic protons upon complexation from $^1H$ NMR spectra.

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