• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Synthesis of Stable Silyl Radicals and Their Application to Multi-spin System

Research Project

Project/Area Number 14340192
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

MATSUMOTO Hideyuki  Gunma University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (90008467)

Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥10,600,000 (Direct Cost: ¥10,600,000)
Fiscal Year 2004: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2003: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥4,900,000 (Direct Cost: ¥4,900,000)
KeywordsSilyl Radical / Silyl Anion / Cyclopolysilane / Ladder Polysilane / Polycyclopolysilane / シリルビラジカル / シアニオン / 開殻化学種 / ラジカル / 安定ラジカル / ポリシラン / ラダーポリシロキサン / アニオンラジカル
Research Abstract

The following results have been obtained on the stabilization, syntheses, and structures and silyl radicals and the related open-shell species.
1)The reduction of bromo[tris(triisopropylsilyl)]silane with alkali metals led to the formation of [tris(triisopropylsilyl)]silyl radical, which was isolated as yellow crystals. The molecular and crystal structure of the silyl radical were determined by X-ray crystallography. It was found that the formation of the stable silyl radical can be carried out in the preparative-scale experiment. The study on the magnetic properties of the silyl radical is underway.
2)trans-1,2,2,3,4,4-Hexa-tert-buy1-1,3-cyclotetrasilanediyl)potassium, which represents the first example of cyclic silyl dianion, was synthesized by the reaction of trans-1,2,2,3,4,4-hexa-tert-buy1-1,3-dibromocyclotetrasilane with potassium in benzene. The X-ray crystallographic analysis of the compound-benzene complex showed a novel supramolecular structure, in which the compound and benzene are stacked alternatively to form an infinite 1-D structure.
3)The silyl-centered biradical, 1,2,2,3,4,4-hexa-tert-buy1-1,3-cyclotetrasilanediyl), was formed as red crystals by the reduction of trans-1,2,2,3,4,4-hexa-tert-buy1-1,3-dibromocyclotetrasilane with potassium in benzene. Studies on the X-ray structure determination and magnetic properties of the crystalline biradical were underway.

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (37 results)

All 2005 2004 2003 2002 Other

All Journal Article (26 results) Book (2 results) Publications (9 results)

  • [Journal Article] Stereoisomers of 1,3,5,7i-Tetrahydroxy-1,3,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal2005

    • Author(s)
      Masafumi Unno, Yasuaki Kawaguchi, Yukiko Kishimoto, Hideyuki.Matsumoto
    • Journal Title

      Journal of the American Chemical Society 127

      Pages: 2256-2263

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Oligocyclic Laddersiloxanes : Alternative Synthesis by Oxidation2005

    • Author(s)
      Masafumi Unno, Ryoji Tanaka, Sumiaki Tanaka, Toshiyuki Takeuchi, Soichiro Kyushin, Hideyuki Matsumoto
    • Journal Title

      Organometallics 24

      Pages: 765-768

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoisomers of 1,3,5,5,7-Tetrahydroxy-1,3,5,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal2005

    • Author(s)
      Msaafumi Unno, Yasuaki Kawaguchi, Yukiko Kishimoto, Hideyuki, Matsumoto
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 2256-2263

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoisomers of 1,3,5,7-Tetrahydroxy-1,3,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal2005

    • Author(s)
      Masafumi Unno, Hideyuki Matsumoto
    • Journal Title

      Journal of the American Chemical Society 127

      Pages: 2256-2263

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Oligocyclic Laddersiloxanes : Alternative Synthesis by Oxidation2005

    • Author(s)
      Masafumi Unno, Hideyuki Matsumoto
    • Journal Title

      Organometallics 24

      Pages: 765-768

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Triisopropylcyclotrisiloxanetriol : An Unprecedented Cyclic Siloxanetriol with Relatively Small Substituents2004

    • Author(s)
      Masafumi Unno, Yukiko Kishimoto, Hideyuki Matsumoto
    • Journal Title

      Organometallics 23

      Pages: 6221-6224

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] (trans- 1,2,2,3,4,4-Hexa-tert-butyl-1,3-cyclotetrasilanediyl)potassium : Supra-molecular Structure of Silylpotassium-Benzene Complex2004

    • Author(s)
      Soichiro Kyushin, Hiroko Kawai, Hideyuki Matsumoto
    • Journal Title

      Organometallics 23

      Pages: 311-313

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The Cyclo[(disilanylene)(butadiyne)]s [(i-Pr)_2Si(i-Pr)_2SiC≡CC≡C]_n(n=2-4)2004

    • Author(s)
      Kesuke Negishi, Masafumi Unno, Hideyuki Matsumoto
    • Journal Title

      Chemistry Letters 33

      Pages: 430-431

    • NAID

      10012847187

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Bicyclic and Tricyclic Ladder Compounds Consisting of Two Oligosiloxane Chains Bridged by Si-Si Rungs2004

    • Author(s)
      Soichiro Kyushin, Masaki Takahashii, Hideyuki Matsumoto
    • Journal Title

      Chemistry Letters 33

      Pages: 24-25

    • NAID

      10011943202

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] オクタシラキュバンの化学2004

    • Author(s)
      海野雅史, 松本英之
    • Journal Title

      有機合成化学協会誌 62

      Pages: 107-115

    • NAID

      10012048941

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] (trans-1,2,2,3,4,4-Hexa-tert-buty1-1,3-cyclotetrasilanediyl)potassium : Supra-molecular Structure of Silylpotassium-Benzene Complex2004

    • Author(s)
      Soichiro Kyushin, Hiroko Kawai, Hideyuki Matsumoto
    • Journal Title

      Organometallics 23

      Pages: 311-313

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The Cyclo[(disilanylene)(butadiyne)]s [(i-Pr)_2Si(i-Pr)_2SiC≡CC≡C]_n( =2-4)2004

    • Author(s)
      Kesuke Negishi, Masafumi Unno, Hideyuki Matsumoto
    • Journal Title

      Chem.Lett. 33

      Pages: 430-431

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Bicyclic and Tricyclic Ladder Compounds Consisting of Two Oligosiloxane Chains Bridged by Si-Si Rungs2004

    • Author(s)
      Soichiro Kyushin, Masaki Takahashi, Hideyuki Matsumoto
    • Journal Title

      Chem.Lett. 33

      Pages: 24-25

    • NAID

      10011943202

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Triisopropylcyclotrisiloxanetriol : An Unprecedented Cyclic Siloxanetriol with Relatively Small Substituents2004

    • Author(s)
      Masafumi Unno, Hideyuki Matsumoto
    • Journal Title

      Organometallics 23

      Pages: 6221-6224

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Bicyclic and Tricyclic Ladder Compounds Consisting of Two Oligosiloxane Chains Bridged by Si-Si Rungs2004

    • Author(s)
      Soichiro Kyushin, Hideyuki Matsumoto
    • Journal Title

      Chemistry Letters 33

      Pages: 24-25

    • NAID

      10011943202

    • Related Report
      2004 Annual Research Report
  • [Journal Article] (trans-1,2,2,3,4,4-Hexa-tert-butyl-1,3-cyclotetrasilanedily) potassium : Supramolecular Structure of the Silylpotassium-Benzene Complex2004

    • Author(s)
      Soichiro Kyushin, Hideyuki Matsumoto
    • Journal Title

      Organometallics 23

      Pages: 311-313

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Structure and Oxidation of Octakis(tert-butyldimethylsilyl)octasilacubane2003

    • Author(s)
      Masafumi Unno, Hideyuki Matsumoto
    • Journal Title

      Journal of Organometallic Chemistry 685

      Pages: 156-161

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] 2,3,6,7,10,11-Hexakis(dimethylsilyl)triphenylene2003

    • Author(s)
      Soichito Kyushin, Norikatsu Takemasa, Hiroshi Horiuchi, Hideyuki Matsumoto
    • Journal Title

      Chemistry Letters 32

      Pages: 1048-1049

    • NAID

      10012821072

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Ladder Polysilanes2003

    • Author(s)
      Soichito Kyushin, Hideyuki Matsumoto
    • Journal Title

      Advances in Organometallic Chemistry 49

      Pages: 133-166

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structure and Oxidation of Octakis(tert-butyldimethylsilyl)octasilacubane2003

    • Author(s)
      Masafumi Unno, Takayoshi Matsumoto, Kikuo Mochizuki, Koichi Higuchi, Midori Goto, Hideyuki Matsumoto
    • Journal Title

      J.Organomet.Chem. 686

      Pages: 175-182

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] 2,3,6,7,10,11-Hexakis(dimethylsilyl)triphenylene2003

    • Author(s)
      Soichiro Kyushin, Norikatsu Takemasa, Hiroshi Horiuchi, Hideyuki Matsumoto
    • Journal Title

      Chem.Lett. 32

      Pages: 1048-1049

    • NAID

      10012821072

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Ladder Polysilanes2003

    • Author(s)
      Soichiro Kyushin, Hideyuki Matsumoto, Ladder Polysilanes
    • Journal Title

      Advances in Organomettalic Chemistry 49

      Pages: 133-166

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Photo-initiated Bromination of Octakis(1,1,2-trimethylpropyl)-octasilacubane with Tetrabromomethane2002

    • Author(s)
      Masafumi Unno, Hiroyuki Masuda, Hideyuki Matsumoto
    • Journal Title

      Silicon Chemistry 1

      Pages: 377-381

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Pentacyclic Laddersiloxane2002

    • Author(s)
      Masafumi Unno, Akiko Suto, Hideyuki Matsumoto
    • Journal Title

      Journal of the American Chemical Society 124

      Pages: 1574-1575

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Photo-initiated Bromination of Octakis(1,1,2-trimethylpropyl)-octasilacubane with Tetrabromomethane2002

    • Author(s)
      Masafumi Unno, Hiroyuki Masuda, Hideyuki Matsumoto
    • Journal Title

      Silicon Chem. 1

      Pages: 377-381

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Pentacyclic Laddersiloxane2002

    • Author(s)
      Masafumi Unno, Akiko Suto, Hideyuki Matsumoto
    • Journal Title

      J.Am.Chem.Soc. 124

      Pages: 1574-1575

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] 21世紀の有機ケイ素化学(玉尾皓平編)分担 第1章6、ケイ素ラジカル、ケイ素カチオンケイ素アニオン。第2章5ラダーポリシラン。第2章6.環状オリゴシラン。2004

    • Author(s)
      松本 英之
    • Publisher
      シーエムシー出版社
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] 21世紀の有機ケイ素科化学:ケイ素ラジカル、ケイ素カチオン、ケイ素アニオン他(分担)2004

    • Author(s)
      松本 英之
    • Total Pages
      316
    • Publisher
      シーエムシー出版
    • Related Report
      2004 Annual Research Report
  • [Publications] Masafumi Unno, Hideyuki Matsumoto: "Structure and Oxidation of Octakis(tert-butyldimethylsilyl)octasilacubane"Journal of Organometallic Chemistry. 685. 156-161 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Soichiro Kyusin, Hideyuki Matsumoto: "2,3,6,7,10,11-Hexakis(dimethylsilyl)triphenylene"Chemistry Letters. 32. 1048-1049 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Soichiro Kyusin, Hideyuki Matsumoto: "Ladder Polysilanes"Advances in Organometallic Chemistry. 49. 133-166 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Soichiro Kyushin, Hideyuki Matsumoto: "Bicyclic and Tricyclic Ladder Compounds of Two Oligosiloxane Chains Bridged by Si-Si Rungs"Chemistry Letters. 33. 24-25 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Soichiro Kyushin, Hideyuki Matsumoto: "(trans-1,2,2,3,4,4-Hexa-tert-butyl-1,3-cyclotetrasilanedily)potassium : Supramolecular Structure of the Silylpotassium-Benzene Complex"Organometallics. 23. 311-313 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] 海野雅史, 松本英之: "オクタシラキュバンの化学"有機合成化学協会誌. 62. 107-115 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Unno, A.Suto, H.Matsumoto: "Pentacyclic Laddersiloxane"J. Am. Chem. Soc. 124. 1574-1575 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Tanaka, S.Kyushin, M.Unno, H.Matsumoto: "Chiral Crystallization of anti-Dodecaisopropyltricyclo-[4.2.0.0^<2,5>]octasilane"Entiomer. 7. 157-159 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Yamada, M.Unno, K.Kobayashi, H.Oku, H.Yamamura, S.Arai, H.Matsumoto, R.Katakai, M.Kawai: "Stereochemistry of Protected Ornithine Side Chains of Gramicidin S Derivatives : X-ray Crystal Structure of the Bis-Boc-tetra-N-methyl Derivatives of Gramicidin"J. Am. Chem. Soc.. 124. 12684-12688 (2002)

    • Related Report
      2002 Annual Research Report

URL: 

Published: 2002-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi