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Synthesis, Structure, and Reactivities of Doubly Bonded Compounds Between Heavier 14 Group Elements and Oxygen

Research Project

Project/Area Number 12440182
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionJapan Women's University

Principal Investigator

OKAZAKI Renji  Japan Women's University, Faculty of Science, Professor, 理学部, 教授 (70011567)

Co-Investigator(Kenkyū-buntansha) TAKENAKA Keiko  Japan Women's University, Faculty of Science, Research Associate, 理学部, 助手 (00130740)
Project Period (FY) 2000 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥14,900,000 (Direct Cost: ¥14,900,000)
Fiscal Year 2003: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2002: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2001: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥5,100,000 (Direct Cost: ¥5,100,000)
Keywordskinetic stabilization / bulky substituent / silanethione / germanethione / silanone / germanone / 典型元素 / X線結晶解析 / ゲルマニウム / ゲルミレン / シリレン
Research Abstract

With the intention of synthesizing the title compounds, we took advantage of a bulky bowl-type substituent, 4-t-butyl-2,6-bis[(2,2",6,6"-tetramethyl-m-terpheny1-2'-yl)methyl]phenyl(Bmt). BmtBr was converted into Bmt(R)GeH_2[R=t-Bu or Tip(2,4,6-triisopropylphenyl)], which were then allowed to react with sulfur to afford Bmt(R)GeS_4(1a : R=t-Bu, 1b:R=Tip).
The desulfurization of la in the presence of 2,3-dimethyl-1,3-butadiene gave a [4+2] adduct of germanethione Bmt(R)Ge=S (2a) with the diene, while the dimer of 2a was obtained in the absence of the diene. By contrast, in the absence of the diene, 1b gave 2b, which is expected to be a good precursor of Bmt(Tip)Ge=O. Similarly, reductive dechlorination of Bmt(Tip)SiCl_2, followed by reaction with sulfur, gave Bmt(Tip)SiS_4 which is expected to be a precursor of Bmt(Tip)Si=S.

Report

(5 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] R.Okazaki: "Heavy ketones, the heavier element congeners of a ketone"Acc.Chem.Res.. 33. 625-630 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Reaction of a Stable Silylene-Isocyanide Complex with Nitrile Oxides : A New Approach to the Generation of a Silanone."Chem.Lett.. 244-245 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Sasamori: "The First Chemical Trapping of Stibibinidene, a Monovalent Antimony Compound"Chem.Lett.. 42-43 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Tokitoh: "Synthesis of Kinetically Stabilized Silaneselone and Silanetellone"Chem.Lett.. 34-35 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Sasamori: "Syntheses, Structures and Properties of Kinetically Stabilized Distibenes and Dibismuthenes, Novel Doubly Bonded Systems between Heavier Group 15 Elements"Bull.Chem.Soc.Jpn.. 75. 661-675 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Synthesis and Properties of the First Stable Silylene-Isocyanide Complexes"Chem.Eur.J.. 9. 3530-3543 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Science of Syntheses, Houben-Weyl Methods of Molecular Transformations, Category 1 Organometallics, Vol.5 Compounds of Group 14 (Ge, Sn, Pb)"George Thieme Verlag : Stuttgart. 59 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Okazaki: "Heavy ketones, the heavier element congeners of a ketone"Acc.Chem.Res.. 33. 625-630 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Reaction of a Stable Silylene-Isocyanide Complex with Nitrile Oxides : A New Approach to the Generation of a Silanone"Chem.Lett.. 244-245 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Sasamori: "The First Chemical Trapping of Stibibinidene, a Monovalent Antimony Compound"Chem.Lett.. 42-43 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Tokitoh: "Synthesis of Kinetically Stabilized Silaneselone and Silanetellone"Chem.Lett.. 34-35 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Sasamori: "Syntheses, Structures and Properties of Kinetically Stabilized Distibenes and Dibismuthenes, Novel Doubly Bonded Systems between Heavier Group 15 Elements"Bull.Chem.Soc.Jpn.. 75. 661-675 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Synthesis and Properties of the First Stable Silylene-Isocyanide Complexes"Chem.Eur.J.. 9. 3530-3543 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Science of Syntheses, Houben-Weyl Methods of Molecular Transformations, Category 1 Organometallics, Vol. 5 Compounds of Group 14 (Ge, Sn, Pb)"George Thieme Verlag : Stuttgart. 27-54 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] N.Takeda: "Synthesis and Properties of the First Stable Silylene-Isocyanide Complexes"Chem.Eur.J.. 9. 3530-3543 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Goto: "Reaction of Stable Sulfenic and Selenenic Acids Containing a Bowl-type Steric Protection Group with a Phosphine. Elucidation of the Mechanism of Reduction of Sulfenic and Selenenic Acids"Chem.Lett.. 32. 1080-1081 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] N.Tokitoh: "Stable 2H-Azasilirene and 2H-Phosphasilirene : Addition Reaction of an Overcrowded Silylene to a Nitrile and a Phosphaalkyne"Silicon Chem.. (in press). (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] N.Takeda: "Science of Syntheses, Houben-Weyl Methods of Molecular Transformations, Category 1 Organometallics, Vol.5 Compounds of Group 14 (Ge, Sn, Pb)"George Thieme Verlag : Stuttgart. 59 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] N.Takeda: "Elemental Sulfur and Sulfur-Rich Compounds II"Springer-Verlag, Berlin. 50 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] N.Tokitoh: "Synthesis of Kinetically Stabilized Silaneselone and Silanetellone"Chem. Lett.. 34-35 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Kishikawa: "Synthesis and Characterization of an Extremely Hindered Tetraaryl-substituted Digermene and Its Unique Properties in the Solid State and in Solution"Polyhedron. 21. 563-577 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Okazaki: "The chemistry of organic germanium, tin and lead compounds, Vol.2"John Wiley & Sons, West Sussex. 98 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Kishikawa: "Synthesis and Characterization of an Extremely Hindered Tetraaryl-substituted Digermene and Its Unique Properties in the Solid State and in Solution"Polyhedron. (in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] R.Okazaki: "Adv. Organomet. Chem., 47"Academic Press, New York. 121-166 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] R.Okazaki: "Heavy Ketones, the Heavier Element Congeners of a Ketone"Acc.Chem.Res.. 33. 625-630 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Takeda: "Reaction of a Stable Silylene-Isocyanide Complex with Nitrile Oxides : A New Approach to the Generation of a Silanone"Chem.Lett.. 244-245 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Wakita: "Crystal Structure of a Stable Silabenzene and Its Photochemical Valence Isomerization into the Corresponding Silabenzvalene"J.Am.Chem.Soc.. 122. 5648-5649 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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