Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Mixed Intramolecular Hydrogen Bonding in Dihydroxythiophene-based Units and Boron and Technetium Chelation

  • Ko, Sang-won (Department of Chemistry and Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Park, Sang-Hyun (Center for HANARO Application Research, Korea Atomic Energy Research Institute) ;
  • Gwon, Hui-Jeong (Center for HANARO Application Research, Korea Atomic Energy Research Institute) ;
  • Lee, Jun-seong (Department of Chemistry and Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Kim, Min-Jeong (Department of Chemistry and Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Kwak, Yeon-ju (Department of Chemistry and Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Do, Young-kyu (Department of Chemistry and Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Churchill, David G. (Department of Chemistry and Molecular Science (BK 21), Korea Advanced Institute of Science and Technology (KAIST))
  • Published : 2006.02.20
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Abstract

Three novel potential metal ion chelating units have been synthesized and characterized: 5-hexylcarbamoyl-3,4-dihydroxythiophene-2-carboxylic acid methyl ester (5), 3-benzyloxy-4-hydroxythiophene-2,5-dicarboxylic acid bis-hexylamide (6), and 3,4-dihydroxythiophene-2,5-dicarboxylic acid bis-hexylamide (7). The crystal structure of 6 was obtained and suggests the presence of three distinct intramolecular hydrogen bonds, namely $[N_{amide}-H{\cdot}{\cdot}{\cdot}O]$ $[O-H{\cdot}{\cdot}{\cdot}O_{amide}]$ and $[N_{amide}-H{\cdot}{\cdot}{\cdot}S]$. Boron chelation with 5, 6 and 7 through the use of $BF_3, \;B(OH)_3 \;or \;B(OMe)_3$ was probed by $^1H$, $^{11}B$, and $^{13}C$ NMR spectroscopy. Technetium (I) chelation with 5, 6 and 7 was also studied via HPLC elutions using $[^{99m}Tc(CO)_3(OH_2)_3]^+$.

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