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Syntheses, Properties, and Reactivities of Unsaturated Ring Compounds Consisting of Silicon and Germanium

Research Project

Project/Area Number 13440185
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

SEKIGUCHI Akira  University of Tsukuba, Department of Chemistry, Professor, 化学系, 教授 (90143164)

Co-Investigator(Kenkyū-buntansha) ICHINOHE Masaaki  University of Tsukuba, Department of Chemistry, Assistant Professor, 化学系, 講師 (90271858)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2003: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2001: ¥7,700,000 (Direct Cost: ¥7,700,000)
KeywordsHeavier Group 1-4 Element / Organosilicon Compound / Organogermanium Compound / Unsaturated Small Ring Compound / Radical Species of Heavier Group 14 Element / Cation Species of Heavier Group 14 Element / Anion Species of Heavier Group 14 Element / Multiple Bond Compounds of Heavier Group 14 Element / 高周期14族元素不飽和環状化合物 / シクロブタジエンジアニオン / シクロブタジエンコバルト錯体 / 有機スズ化合物 / 高周期14族元素不飽和小員環化合物 / 14族元素多重結合化合物 / シリルカチオン / シリルラジカル / シリルアニオン / ケイ素π電子系化合物
Research Abstract

We have studied the reactivity of unsaturated small ring compound consisting of heavier Group 14 Elements such as silicon and germanium. The following results have been obtained in this project
(1)The Reaction of Cyclotrisilene : Synthesis and Structure of Cyclotetrasilenylium Ion
The reaction of ^tBu_2MeSi-substituted cyclotrisilene with [Et_3Si(C_6H_6)]^+・TPFPB^-in benzene gave cyclotetrasilenylium・TPFPB^-(TPFPB-=(C_6F_5)_4B^-) as air-and moisture-sensitive yellow crystals. X-ray crystallography revealed that the cyclotetrasilenylium ion is not only a free cation without the Interaction with counter anion and solvent molecules, but a 2π-electron homoaromatic compound consisting of silicon
(2)Reactivities of Cyclotetrasilenylium Ion : Synthesis and Structure of Cyclotetrasilenyl Radical and Cyclotetrasilenylide Ion
The reaction of the Cyclotetrasilenylium ion^-with bulky trialkylsilylsodium afforded cyclotetrasilenyl radical as a stable crystalline compound through the one electron reduct … More ion. The crystallographic analysis reveals that the cyclotetrasilenyl radical is a free silyl radical, having an allyl type delocalized structure, without any intermolecular interaction. Two electron reduction of the Cyclotetrasilenylium ion was also achieved by Li, Na, and KC_8 in diethyl ether to give cyclotetrasilenide ion. Stepwise chemical oxidation of cyclotetraslienid successfully regenerates the cyclotetrasilenyl radical and the Cyclotetrasilenylium Ion, indicating that cyclotetrasilenyl cation, radical, and anion show chemically reversible two electron redox system on the allyl type silicon π-electron system
(3)The Reaction of Disilagermirene with Divalent Species of Germanium and Tin
Disilagermirene derivatives with Si=Si or Si=Ge double bond react with dichlorogermylene-1,4 dioxane complex to give disiladigermetene, which have an endocyclic Ge=Ge double bond. The same type ring expansion took place in the reaction of disilagermirenes with dichlorostannylene-1,4 dioxane complex to afford unsaturated four membered ring compound bearing Ge=Sn double bond Less

Report

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

    (42 results)

All Other

All Publications (42 results)

  • [Publications] Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"Journal of the American Chemical Society. 123・22. 5356-5357 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi: "Cyclotetrasilenyl : The First Isolable Silyl Radical"Journal of the American Chemical Society. 123・49. 12346-123437 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"Journal of the American Chemical Society. 124・7. 1158-1159 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi: "Isolable Silyl and Germyl Radicals Lacking Conjugation with π-Bonds : Synthesis, Characterization, and Reactivity"Journal of the American Chemical Society. 124・33. 9865-9869 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi: "Bis(tri-tert-butylsilyl)silylene : Triplet Ground State Silylene"Journal of the American Chemical Society. 125・17. 4962-4963 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi: "Tin-Centered Radical and Cation : Stable and Free"Journal of the American Chemical Society. 125・31. 9250-9251 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi: "The Chemistry of Organic Germanium, Tin an Lead Compound"John Wiley & Sons, Ltd. 28 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kazuyuki Ishii, Nagao Kobayashi, sukasa Matsuo, Masanobu Tanaka, Akira Sekiguchi: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"J.Am.Chem.Soc.. 123. 5356-5357 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Tadahiro Matsuno, Masaaki Ichinohe: "Cyclotetrasilenyl : he first Isolable Silyl Radical"J.Am.Chem.Soc.. 123. 12436-12437 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Yutaka Ishida, Norihisa Fukaya, Masaaki Ichinohe, Nozimi Takagi, Shigeru Nagase: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"J.Am.Chem.Soc.. 124. 1158-1159 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Yutaka Ishida, Yoshio Kabe, Masaaki Ichinohe: "The Cation Cluster of Heavier Group 14 Elements : A Free Germyl Canon with Trishomoaromatisity"J.Am.Chem.Soc.. 124. 8766-8767 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Tomohide Fukawa, Masaaki Nakamoto, Vladimir Ya.Lee, Masaaki Ichinohe: "Isolable Silyl and Germyl Radicals Lacking Conjugation with n-Bonds : Synthesis, Characterization, and Reactivity"J.Am.Chem.Soc.. 124. 9865-9869 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Vladimir Ya.Lee, Masaaki Ichinohe, Akira Sekiguchi: "2,4-Disila-l-germatricyclo[2.1.0.0^<2.5>]pentane : A New Type Cage Compound of Group 14 Elements with an Extremely Long Ge-C Bridge Bond and an "Umbrella"-Type Configuration of a Ge Atom"J.Am.Chem.Soc.. 124. 9962-9963 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Giinther Maier, Jorg Neudert, Oliver Wolf, Dirk Pappusch, Akira Sekiguchi, Masanobu Tanaka, Tsukasa Matsuo: "Tetrakis(trimethylsilyl)tetrahedrane"J.Am.Chem.Soc.. 124. 13819-13826 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Rika Izumi, Vladimir Ya.Lee, Masaaki Ichinohe: "The First Silastannene >Si=Sn< : A New Doubly-Bonded System of Heavier Group 14 Elements"J.Am.Chem.Soc.. 124. 14822-14823 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masaaki Nakamoto, Tomohide Fukawa, Vladimir Ya.Lee, Akira Sekiguchi: "Nearly Planar Non-Solvated Monomeric Silyl-and Germyllithiums as a Result of Intramolecular CH-Li Agostic Interaction"J.Am.Chem.Soc.. 124. 15160-15161 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Rika Izumi, Shinji Ihara, Masaaki Ichinohe, Vladimir Ya.Lee: "The First Isolable 1,1-Dilithiogermane and its Unusual Dimeric Structure -a New Effective Reagent for the Preparation of Doubly-Bonded Derivatives of Group 14 Elements"Angew.Chem., Int.Ed.. 41. 1598-1600 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Vladimir Ya.Lee, Kazunori Takanashi, Masaaki Ichinohe, Akira Sekiguchi: "A Chemical Trick : How to Make a Digermene from a Disilene. Formation of ^3Δ-1,2,3,4-Disiladigermetene"J.Am.Chem.Soc.. 125. 6012-6013 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Takashi Tanaka, Masaaki Ichinohe, Kimio Akiyama, Shozo Tero-Kubota: "Bis(tri-tert-butylsilyl)silylene : Triplet Ground State Silylene"J.Am.Chem.Soc.. 125. 4962-4963 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Tomohide Fukawa, Vladimir Ya.Lee, Masaaki Nakamoto: "Tin-Centered Radical and Cation : Stable and Free"J.Am.Chem.Soc.. 125. 9250-9251 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yutaka Ishida, Akira Sekiguchi, Yoshio Kabe: "The 1,4,5-Trigermabicyclo[2.1.0]pent-2-en-5-ylium : The Isolable Bishomocyclopropenylium Ion Containing Heavier Group 14 Element"J.Am.Chem.Soc.. 125. 11468-11469 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Akira Sekiguchi, Masanobu Tanaka: "Tetrahedranyllithium : Synthesis, Characterization, and Reactivity"J.Am.Chem.Soc.. 125. 12684-12685 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masaaki Ichinohe, Masafumi Toyoshima, Rei Kinjo, Akira Sekiguchi: "Tetrasilatetrahedranide : The First Silicon Cage Anion"J.Am.Chem.Soc.. 125. 13328-13329 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"Journal of the American Chemical Society. 123・22. 5356-5357 (2001)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akira Sekiguchi: "Cyclotetrasilenyl : The First Isolable Silyl Radical"Journal of the American Chemical Society. 123・49. 12346-123437 (2001)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akira Sekiguchi: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"Journal of the American Chemical Society. 124・7. 1158-1159 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akira Sekiguchi: "Isolable Silyl and Germyl Radicals Lacking Conjugation with π-Bonds : Synthesis, Characterization, and Reactivity"Journal of the American Chemical Society. 124・33. 9865-9869 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akira Sekiguchi: "Bis(tri-tert-butylsilyl)silylene : Triplet Ground State Silylene"Journal of the American Chemical Society. 125・17. 4962-4963 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akira Sekiguchi: "Tin-Centered Radical and Cation : Stable and Free"Journal of the American Chemical Society. 125・31. 9250-9251 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akira Sekiguchi: "The Chemistry of Organic Germanium, Tin an Lead Compound"John Wiley & Sons, Ltd. 28 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masaaki Nakamoto: "Nearly Planar Non-Solvated Monomeric Silyl-and Germyllithiums as a Result of Intramolecular CH-Li Agostic Interaction"Journal of the American Chemical Society. 124・51. 15160-15161 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Vladimir Ya.Lee: "2.4-Disila-1-gcrmatricyclo[2.1.0.02,5]pentane : A New Type Cage Compound of Group 14 Elements with an Extremely Long Ge-C Bridge Bond and an "Umbrella"-Type Configuration of a Ge Atom"Journal of the American Chemical Society. 124・34. 9962-9963 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tadahiro Matsuno: "Cyclotetrasilenide Ion : A Reversible Redox System of Cyclotetrasilenyl Cation, Radical, and Anion"Angewandte Chemie, International Edition. 41・9. 1575-1577 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akira Sekiguchi: "The First Isolable 1,1-Dilithiogermane and its Unusual Dimeric Structure-a New Effective Reagent for the Preparation of Doubly-Bonded Derivatives of Group 14 Elements"Angewandte Chemie, International Edition. 41・9. 1598-1600 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akira Sekiguchi: "(^1Bu_2MeSi)_3Ge^+ : An Isolable Free Germyl Cation Lacking Conjugation to π-Bonds"Angewandte Chemie, International Edition. 42・10. 1143-1145 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Akira Sekiguchi: "Aromaticity of the Cyclobutadiene Dianion : Structural Characteristics and MagneticProperties"Organometallics. 21・6. 1072-1076 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"Journal of the American Chemical Society. 123・22. 5356-5357 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Akira Sekiguchi: "Cyclotetrasilenyl: The First Isolable Silyl Radical"Journal of the American Chemical Society. 123・49. 12436-12437 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Akira Sekiguchi: "From a Cyclobutadiene Dianion to a Cyclobutadiene : Synthesis and Structural Characterzation of Tetrasilyl-Substituted Cyclobutadiene"Angewandte Chemie,International Edition. 40・9. 1675-1677 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Fukaya Norihisa: "Ring Contraction of 1,2-Digermacyclohexa-1,4-diene to (Germacyclopent-3-enyl)germylene"Organometallics. 20・16. 3364-3366 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masaaki Ichinohe: "A New Approach to the Synthesis of Unsymmetrical Disilenes and Germasilene: Unusual ^<29>Si NMR Chemical Shifts and Methanol Addition with Unexpected Regiospecificity"Organometallics. 20・20. 4141-4143 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Vladimir Ya. Lee: "Reaction of Disilagermirenes with Phenylacetylene: From a Germasilene -Ge=Si- to a Metalladiene of the Type -Si=Ge-C=C"Journal of Organometallic Chemistry. 636・. 42-49 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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