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Basic Studies on Photo- and Thermal-Reactions of 14 Group Metal Compounds

Research Project

Project/Area Number 02640387
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionUniversity of Electro-Communications

Principal Investigator

NAKADAIRA Yasuhiro  University of Electro-Comunications Faculty of Electro-Communications, Professor, 電気通信学部, 教授 (90004332)

Co-Investigator(Kenkyū-buntansha) KAKO Masahiro  University of Electro-Comunications Faculty of Electro-Communications, Research, 電気通信学部, 助手 (10233678)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1991: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1990: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsPhotolysis / 185 nm photochmistry / Organosilicon compound / Mass spectroscopy / Silyl radical / Photo-induced electron transfer / Silylene / Organogermanium compound / テトラアルキルシラン / シリレン / シリルラジカル / ポリシラン / アリ-ル置換14族カテナ-ト / オクタメチルトリシラン
Research Abstract

1.185 nm photolysis of octamethyltrisilane, hexamethyldisilane, and tetrabutylsilane
In the trisilane, elimination of dimethylsilylene competes favorably with homolysis of Si-Si bonds. In the disilane, homolysis of the Si-Si bond prevails over silylene generation, which is confirmed by detection of tetramethylsilane and the trapping experiment. In the monosilane, cleavage of Si-C bonds predominates but a trac7e of dibutylsilylene is detected by the trapping experiment.
2.185 nm photolysis of hexamethyldigermane
Photochemical behavior of the digermane has been shown t'o be qu ite similar to those of the 'corresponding silicon analog, but the elimination of the divalent species is much more effective in the germanium analog.
3. Photolysis of aryl-substituted 14 group metal catenates, PhMe_2E-E'Me_3 (E, E' = Si, Ge)
Photolysis of PhMe_2SiGeMe_3, PhMe_2GeSiMe_3, and PhMe_2GeGeMe_3 have been examined. Their photochemical behavior can be rationalized by the radical pair generated by homolysis of the E-E' bond.
4. Analogy between photo-induced electron transfer reaction and the mass spectral fragmentation
Mass spectra of polysilaalkanols are rationalized based on their chemical reactivities under photo-induced electron transfer conditions.
5. Photo-induced transfer reaction of trifluoromethyl-substituted benzenes with hexamethyldisilane and octamethyltrisilane
Under these conditions, substitution of the fluorine with the silyl function, and silylation of the aromatic ring have shown to take place.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] K.Mochida: "Phtochemical reactions of arly-substituted catenates of group 4B elements,PhMe_2E-E'Me_3(E,E'=Si and Ge).Formation of a radical pair" J.Organomet.Chem.412. 9-19 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Mochida: "Photochemcal reactons of vinyl-,styryl-,and benzyl- Substituted digermanes" Bull.Chem.Soc.Jpn.2772-2777 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nakadaira: "Photo-induced electron transfer reaction of polysilane.Intermolecular trapping of a transient silyl radical cation with a nucleople" Chem.Lett.327-330 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nakadaira: "Mass spectral fragmentations of polysilaalkanols.The analogies between mass spectrometry and photo-induced electron transfer" Chem.Lett.601-602 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Mochida: "Photochemical reactions of arylsubstituted catenates of group 4B elements, PhMe_2E-E'Me_3 (E, E' = Si and Ge). Formation of a radical pair" J. Organomet. Chem.412. 9-19 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Mochida: "Photochemical reactions of vinyl-, styryl-, and benzyl- Substituted digermanes" Bull. Chem. Soc. Jpn.64. 2772-2777 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nakadaira: "Photo-induced electron transfer reaction of polysilane. Intramolecular trapping of a transient silyl radical cation with a nucleophle" Chem. Lett.327-330 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nakadaira: "Mass spectral fragmentations of polysilaalkanols. The analogies between mass spectrometry and photo-induced elecron transfer" Chem. Lett.601-602 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Mochida: "Photochemical reactions of vinylー,styrylー,and benzylーSubstituted digermanes" Bull.Chem.Soc.Jpn.64. 2772-2777 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Nakadaira: "Photoーinduced electron transfer reaction of polysilane.Intramolecular trapping of a transient silyl radical cation with a nucleophle" Chem.Lett.327-330 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Nakadaira: "Mass spectral fragmentations of polysilaalkanols.The analogies between mass spectromery and photoーinduced elecron transfer" Chem.Lett.601-602 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Kunio Mochida: "Photochemical Reactions of Arylーsubstituted Catenates of Group 4B Elements,PhMe_2EーE'Me_3(E,E'=Si and Ge).Formation of a Radical Pair." J.Organomet.Chem.(1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yasuhiro Nakadaira: "Mass Pectral Fragmentations of Polysilanylalkanols.The Analogies between Mass Spectrometry and PhotoーInduced Electron Transfer." Chem.Lett.(1991)

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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