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Synthesis of Polysilanes by Electrochemical Reactions.

Research Project

Project/Area Number 03453104
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionHIROSHIMA UNIVERSITY

Principal Investigator

ISHIKAWA Mitsuo  Hiroshima Univ., Fac. of Eng., Professor, 工学部, 教授 (20025985)

Co-Investigator(Kenkyū-buntansha) KUNAI Atsutaka  Hiroshima Univ., Fac. of Eng., Associate Professor, 工学部, 助教授 (90029190)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥6,600,000 (Direct Cost: ¥6,600,000)
Fiscal Year 1992: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1991: ¥4,500,000 (Direct Cost: ¥4,500,000)
KeywordsElectrolytic Reduction of Chlorosilanes / Copper Electrodes / Synthesis of Polysilanes / Disilanylene Polymer / Chlorination of Hydrosilanes / CuCl_2-CuI Reagent / 電解還元 / クロロシラン / ジシラニレンポリマ-
Research Abstract

Synthesis of polysilanes by electrochemical method has been investigated. Cathodic reduction of chlorosilanes with the use of copper electrode system in dimethoxyethane in an undivided cell afforded some lower homologues of polysilanes such as disilanes, trisilanes, tetrasilanes, and pentasilanes selectively in high yields. Similar electrolyses of 1,2-bis(chloromethylphenylsilyl)ethane and 1,2-bis[chloromethyl(rho-tolyl)silyl]ethane afforded poly(disilanylene)ethylenes with high molecular weights, in which no siliconoxygen bonds in the polymer backbone are included. Moreover, reduction of 1,2-bis- (chloromethylphenylsilyl)benzene afforded poly(disilanylene)phenylene.
A highly selective synthesis of chlorosilanes from hydrosilanes has also been investigated. The reaction of dimethylphenylsilane, methyldiphenylsilane, and di(n-butyl)- methylsilane with 2 equiv of copper(II) chloride and a catalytic amount of copper(I) iodide afforded the respective triorganochlorosilanes. Similar reactions of polyhydrosilanes such as diethylsilane, methylphenylsilane, phenylsilane, 1,1,2,2-tetraethyldisilane, and 1,2- dimethyl-1,2-diphenyldisilane with 2 equiv of the CuCl_2(CuI) reagent gave the corresponding monochlorinated hydrosilanes selectively, while treatment with 4 equiv of the reagent afforded dichlorosilanes as the sole product.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.1.Synthesis of Di- and Trisilanes with Use of Mercury and Silver Electrode Systems" Organometallics. 10. 893-895 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.2.Synthesis of Polysilane Oligomers by a Copper Electrode System" Organometallics. 10. 2001-2003 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.3.Synthesis of Poly(disilanylene)ethylenes by Electrolysis of Bis(chlorosilyl)ethanes" Organometallics. 11. 2899-2903 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka KUNAI: "Highly Selective Synthesis of Chlorosilanes from Hydrosilanes" Organometallics. 11. 2708-2711 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 石川 満夫(監修): "有機ケイ素戦略資料,第1集" サイエンスフォーラム, 515 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 石川 満夫: "新しい有機ケイ素ポリマー" 共立出版, 80 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Electrochemistry of Organosilicon Compounds. 1. Synthesis of Di- and Trisilanes with Use of Mercury and Silver Electrode Systems" Organometallics. 10. 893-895 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Electrochemistry of Organosilicon Compounds. 2. Synthesis of Polysilane Oligomers by a Copper Electrode System" Organometallics. 10. 2001-2003 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Electrochemistry of Organosilicon Compounds. 3. Synthesis of Poly(disilanylene)-ethylenes by Electrolysis of Bis(chlorosilyl)-ethanes" Organometallics. 11. 2899-2903 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Highly Selective Synthesis of Chlorosilanes from Hydrosilanes" Organometallics. 11. 2708-2711 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.3.Synthesis of Poly(disilanylene)ethylenes by Electrolysis of Bis(chlorosilyl)ethanes" Organometallics. 11. 2899-2903 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Atsutaka KUNAI: "Highly Selective Synthesis of Chlorosilanes from Hydrosilanes" Organometallics. 11. 2708-2711 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.1.Synthesis of Diーand Trisilanes by Mercury and Silver Electrode Systems." Organometallics. 10. 893-895 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.2.Synthesis of Polysilane Oligomers by Copper Electrode System." Organometallics. 10. 2001-2003 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Atsutaka KUNAI: "Highly Selective Synthesis of Chlorosilanes from Hydrosilanes." Organometallics. 11. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.3.Synthesis of Poly(disilanylene)ethylenes," Organometallics. 11. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 石川 満夫(監修): "有機ケイ素戦略資料,第1集" サイエンスフォ-ラム, 515 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 石川 満夫: "新しい有機ケイ素ポリマ-" 共立出版, 80 (1991)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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