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2000 Fiscal Year Final Research Report Summary

The Chemistry of Inter-element Unsaturated Linkage

Research Project

Project/Area Number 09239101
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

YOSHIFUJI Masaaki  Tohoku University Graduate School of Science, Professor, 大学院・理学研究科, 教授 (90011676)

Co-Investigator(Kenkyū-buntansha) KAWASHIMA Takayuki  University of Tokyo Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (80011766)
SEKIGUCHI Akira  University of Tsukuba Institute of Chemistry, Professor, 化学系, 教授 (90143164)
KIRA Mitsuo  Tohoku University Graduate School of Science, Professor, 大学院・理学研究科, 教授 (40004452)
NAGASE Shigeru  Tokyo Metropolitan University Graduate School of Science, Professor, 大学院・理学研究科, 教授 (30134901)
TOKITOH Norihiro  Kyoto University Institute of Chemical Research, Professor, 化学研究所, 教授 (90197864)
Project Period (FY) 1997 – 2000
Keywordssteric protection / spiropentasiladiene / aromatic compound / ineterelement double bond / multiple bond / theoretical chemistry / intramolecular coordination / pentavalent 1, 2-oxasilatanide
Research Abstract

1. Desulfurization reaction of a dithioxophosphorane bearing the 2,4-di-t-butyl-6-methylphenyl group as protecting moiety gave the corresponding dithioxophosphine, which slowly trimerized to trithiatriphosphinane and isolated.
2. Photoisomerization of a 1-tris (trialkylsilyl) cyclotrisilene proceeded to give the corresponding bicyclo [1.1.0] tetrasilane, and the addition of an alcohol occurred in the anti-addition mode. Furthermore, as byproduct, the spiropentasiladiene derivative was isolated and characterized.
3. A cyclotrigermenium ion, constituting the 3-membered 2-π electron aromatic system, reacted with a bulky nucleophile to give a cyclotrigermene, unsymmetrically substituted at the saturated germanium atom. It was found that the conformation around the double bond depends on the electronic and steric effects of the substituent.
4. Thermal reaction of penta-coordinated 1,2-oxasiletanides bearing the Martin ligand were studied in the presence of acetic acid or 1, 1, 1-trifluoroethanol as proton source. 1,2-Oxasiletanides is considered to be a reaction intermediate, which serves for the Peterson reaction and the homo-Brook rearrangement depending upon the bulkiness at the 3-position as well as the acidity of the proton source.
5. Utilizing the 2,6-bis [bis (trimethylsilyl) methyl)-4-[tris (trimethylsilyl) methyl] phenyl group, a novel stibabismuthene as a double bond compound between two different group 15 elements, was prepared and characterized.
6. Taking the electronic and steric effect of substituents into account, a real triple bond compounds of silicon, disilyne, has been proposed to be stabilized, by theoretical calculation. Similarly triple bonds containing germanium, tin, and lead ware calculated as well as silanaphthalene and silabenzene.

  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] S.Ito, H.Sugiyama, M.Yoshifuji: "Isolation of a Kinetically Stabilized 1,3,6-Triphosphafulvene"Angew.Chem.Int.Ed.. 39. 2781-2783 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Iwamoto, M.Tamura, C.Kabuto, M.Kira: "A stable bicyclic compound with two Si=Si double bonds"Science. 290. 504-506 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Sekiguchi, T.Matsuno, M.Ichinohe: "The Homocyclotrisilenylium Ion : A Free Silyl Cation in the Condensed Phase"J.Am.Chem.Soc.. 122. 11250-11251 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Kano, X.J.Hua, S.Kawa, T.Kawashima: "Synthesis, Structure, and Thermolysis of Pentacoordinate 1,3,2λ^5-Oxaza-phosphetidines : The Intermediates of Aza-Wittig Reactions"Tetrahedron Lett.. 41. 5237-5241 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Sasamori, N.Takeda, and N.Tokitoh: "Synthesis of a Stable Stibabismuthene ; The First Compound with an Antimony-Bismuth Double Bond"Chem.Commun.. 1353-1354 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Nagase, K.Kobayashi, N.Takagi: "Triple Bonds between Heavier Group 14 Elements. A Theoretical Approach"J.Organomet.Chem.. 611. 264-271 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Tokitoh, W.Ando: "Thiireutes, Selenirenes, and Tellurireutes. In Science of Syntheses, Houben-Weyl Methods of Molecular Transformations"George Thieme Velag, Stuttgart. 23 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Ito, H.Sugiyama, M.Yoshifuji: "Isolation of a Kinetically Stabilized 1,3,6-Triphosphafulvene"Angew.Chem.Int.Ed. 39. 2781-2783 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Iwamoto, M.Tamura, C.Kabuto, M.Kira: "Astable bicyclic compound with two Si=Si double bonds"Science. 290. 504-506 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sekiguchi, T.Matsuno, M.Ichinohe: "The Homocyclotrisilenylium Ion : A Free Silyl Cation in the Condensed Phase"J.Am.Chem.Soc. 122. 11250-11251 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Kano, X.J.Hua, S.Kawa, T.Kawashima: "Synthesis, Structure, and Thermolysis of Pentacoordinate 1,3,2λ^5-Oxaza-phosphetidines : The Intermediates of Aza-Wittig Reactions"Tetrahedron Lett.. 41. 5237-5241 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Sasamori, N.Takeda, and N.Tokitoh: "Synthesis of a Stable Stibabismuthene ; The First Compound with an Antimony-Bismuth Double Bond"Chem.Commun.. 2000. 1353-1354 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Nagase, K.Kobayashi, N.Takagi: "Triple Bonds between Heavier Group 14 Elements. A Theoretical Approach"J.Organomet.Chem. 611. 264-271 (2000)

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

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Published: 2002-03-26  

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