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2006 Fiscal Year Final Research Report Summary

Construction of functional supramolecules based on the electronic properties of heteroatoms and nonalternant conjugation

Research Project

Project/Area Number 16550040
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionYamaguchi University

Principal Investigator

MURAFUJI Toshihiro  Yamaguchi University, Graduate School of Medicine, Associate Professor, 大学院医学系研究科, 助教授 (40253140)

Project Period (FY) 2004 – 2006
KeywordsHeteroatom / Nonalternant conjugation / Supramolecule / Azulene / Bismuth / Antimony / Phosphorus / Hypervalency
Research Abstract

A nonaltemant organyl ligand derived from azulene, a 1,3-dichloro-2-azulenyl group, is introduced for the first time into the bismuth and antimony center. Conversion of the azulenylbismuthanes into the pentacoordinated difluorides by xenon difluoride promotes the π-polarization of the azulene nucleus, which is detected as a color change in solution as well as changes in the chemical shifts of the ^<13>C NMR spectra. Similar tendency is observed in the antimony congeners. The X-ray crystallographic study of (1,3-dichloro-2-azulenyl)diphenylbismuth difluoride reveals that the intermolecular π-π stacking takes place between the azulenyl groups through the interaction of the five-membered ring with the seven-membered ring. This may reflect the more polarized azulenyl group of the difluorides, which strengthens the stacking interaction.
(1,3-Dihalo-2-azulenyl)diphenylphosphines [halogen=Cl,Br] have been synthesized, and the effect of the nonaltemant azulenyl group on the reactivity and properties of these phosphines has been studied in comparison with that of the group 15 congeners. The electronic structure of the nonalternant conjugation is dramatically affected by the change in the valency at the phosphorus. Thus, oxidation of the azulenyldiphenylphosphines with hydrogen peroxide proceeded with a dramatic color change from green to blue, giving the corresponding phosphine oxides. The ^<13>C NMR study shows the enhanced π-polarization in the azulenyl group of the phosphine oxides compared to that of the parent phosphines, but the degree is not as marked as that observed in the bismuth and antimony systems. Azulenylphosphine oxide has head-to-tail π-π stacking in crystals, reflecting the enhanced π-polarization in the high oxidation state of the phosphorus center.

  • Research Products

    (10 results)

All 2007 2006 2005 2004

All Journal Article (10 results)

  • [Journal Article] Characterization of azulenylphosphine derivatives. Unexpected debromination and its synthetic utility in the preparation of 2-substituted azulene2007

    • Author(s)
      A.F.M.Mustafizur Rahman et al.
    • Journal Title

      Organometallics 26 (12)(未定)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Characterization of azuylenylphosphine derivatives. Unexpected debromination and its synthetic utility in the preparation of 2-substituted azulene.2007

    • Author(s)
      A.F.M.Mustafizur Rahman, T.Murafuji, T.Shibasaki, K.Suetake, K.Kurotobi Y.Sugihara
    • Journal Title

      Organometallics Vol 26 (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Inhibition of Jack bean urease by organobismuth compounds2006

    • Author(s)
      T.Murafuji et al.
    • Journal Title

      Bioorganic & Medicinal Chemistry Letters 16

      Pages: 1510-1513

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Inhibition of jack bean urease by organobismuth compounds.2006

    • Author(s)
      T.Murafuji, T.Azuma, Y.Miyoshi, M.Ishibashi, A.F.M.Mustafizur Rahman, K.Migita, Y.Sugihara, Y.Mikata
    • Journal Title

      Bioorg. & Med.Chem.Lett. Vol 16

      Pages: 1510-1513

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Chlorination of p-substituted triarylpnictogens by sulfuryl chloride : Difference in the reactivity and spectroscopic characteristics between bismuth and antimony2005

    • Author(s)
      A.F.M.Mustafizur Rahman et al.
    • Journal Title

      Journal of Organometallic Chemistry 690

      Pages: 4280-4284

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Chlorination of p-substituted triarylpnictogens by sulfuryl chloride. Difference in the reactivity and spectroscopic characteristics.2005

    • Author(s)
      A.F.M.Mustafizur Rahman, T.Murafuji, M.Ishibashi, Y.Miyoshi, Y.Sugihara
    • Journal Title

      J.Organomet.Chem. Vol 690

      Pages: 4280-4284

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] First introduction of an azulenyl group into the bismuth and antimony center. Synthesis and structure of azulenylbismuthanes and their difluorides2004

    • Author(s)
      A.F.M.Mustafizur Rahman et al.
    • Journal Title

      Organometallics 23(26)

      Pages: 6176-6183

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Effect of π-accepting substituent on the reactivity and spectroscopic characteristics of triarylbismuthanes and triarylbismuth dihalides2004

    • Author(s)
      A.F.M.Mustafizur Rahman et al.
    • Journal Title

      Journal of Organometallic Chemistry 689

      Pages: 3395-3401

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Effect of π-accepting substituent on the reactivity and spectroscopic characteristics of triarylbismuthanes and triarylbismuth dihalides.2004

    • Author(s)
      A.F.M.Mustafizur Rahman, T.Murafuji, M.Ishibashi, Y.Miyoshi, Y.Sugihara
    • Journal Title

      J.Organomet.Chem. Vol 689

      Pages: 3395-3401

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] First introduction of an azulenyl group into the bismuth and antimony center. Synthesis and structure of azulenylbismuthanes and their difluorides.2004

    • Author(s)
      A.F.M.Mustafizur Rahman, T.Murafuji, K.Kurotobi, Y.Sugihara, N.Azuma
    • Journal Title

      Organometallics Vol 23

      Pages: 6176-6183

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2008-05-27  

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