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Development of Isolable Group-14 Element Species That Contains a Single Pi-Bonding

Research Project

Project/Area Number 20K21185
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionTohoku University

Principal Investigator

Iwamoto Takeaki  東北大学, 理学研究科, 教授 (70302081)

Project Period (FY) 2020-07-30 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2021: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Fiscal Year 2020: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Keywordsπ結合 / 高歪化合物 / 単結合 / 高歪み化合物 / π電子系 / ケイ素 / 反応 / 炭素 / 共役
Outline of Research at the Start

本研究では、π結合のみからなる単結合(π型単結合)を持つ安定なケイ素および炭素化合物を合成し、その分子構造と性質及び反応性を明らかにすることで、π型単結合の特徴を理解することを目的とする。π型単結合は、多重結合に見られるπ結合とは異なりσ結合を伴わない高活性な結合である。本研究ではこのπ型単結合を特異なπ電子系ユニットとして位置付け、新しいπ電子系の化学を発展させる。

Outline of Final Research Achievements

In this study, we synthesized a stable bicyclo[1.1.0]tetrasilane derivatives as an isolable silicon compound with a pi-type single bond, and disclosed their molecular structures by using X-ray single crystal crystallographic analysis and various spectra. We have also synthesized compounds in which a planar bicyclo[1.1.0]tetrasilane unit is incorporated into organic pi-electron compounds. The UV-visible absorption spectra and theoretical calculations indicate that the pi-type silicon-silicon single bond affects pi-conjugation and that the pi-type silicon-silicon single bond without an underlying sigma bond can serve as a unit of the pi-conjugated system.

Academic Significance and Societal Importance of the Research Achievements

π結合は有機分子に多様な構造、反応性と機能を付与する重要な化学結合である。一般に有機分子ではπ結合は二重結合や三重結合などの多重結合に見られ、骨格を維持するσ結合を伴う。本研究ではσ結合を伴わないπ結合を持つ安定ケイ素化合物が合成可能であることを示し、その分子構造や電子状態を明らかにした。これまで機能を持った有機π電子化合物が多数合成されているが、そのほとんどはπ結合の緻密な組み合わせやその変形によるものである。本研究はσ結合を伴わないπ型ケイ素-ケイ素単結合がπ共役系の単位になることを明らかにした。

Report

(5 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (22 results)

All 2023 2022 2021 2020

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (16 results) (of which Int'l Joint Research: 2 results,  Invited: 8 results)

  • [Journal Article] Synthesis, Structure and Electronic Properties of a Stable π‐Type 3‐Electron‐2‐Center‐Bonded Species: A Silicon Analogue of a Bicyclo[1.1.0]butane Radical Anion2022

    • Author(s)
      Koike Taichi、Osawa Raiki、Ishida Shintaro、Iwamoto Takeaki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: e202117584 Issue: 20 Pages: 1-6

    • DOI

      10.1002/anie.202117584

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] An Isolable 2,4-Diaminotetrasilabicyclo[1.1.0]but-1(3)-ene: Effects of Amino Groups at the Bridge Positions2022

    • Author(s)
      Koike Taichi、Honda Shunya、Iwamoto Takeaki
    • Journal Title

      Chemistry Letters

      Volume: 51 Issue: 1 Pages: 77-80

    • DOI

      10.1246/cl.210595

    • NAID

      130008137580

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] π-Conjugated species with an unsupported Si-Si π-bond obtained from direct π-extension2021

    • Author(s)
      Nukazawa Takumi、Iwamoto Takeaki
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 76 Pages: 9692-9695

    • DOI

      10.1039/d1cc04332c

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Reduction of a Bicyclo[1.1.0]tetrasil-1(3)-ene with LiAlH4 Leading to an Isolable Cyclotrisilenide2021

    • Author(s)
      Nukazawa Takumi、Iwamoto Takeaki
    • Journal Title

      Organometallics

      Volume: 40 Issue: 21 Pages: 3511-3515

    • DOI

      10.1021/acs.organomet.1c00521

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of an NHC-Coordinated Dialkyldisilavinylidene and Its Oxidation Providing a Silicon Analog of an Acetolactone2021

    • Author(s)
      Kobayashi Ryo, Ishida Shintaro, and Iwamoto Takeaki
    • Journal Title

      Organometallics

      Volume: 40 Issue: 7 Pages: 843-847

    • DOI

      10.1021/acs.organomet.1c00130

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Interconversion between a planar 1,3-dichlorobicyclo[1.1.0]tetrasilane and a (chloro)(chlorosilyl)cyclotrisilene2020

    • Author(s)
      Nukazawa Takumi and Iwamoto Takeaki
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 46 Pages: 16728-16735

    • DOI

      10.1039/d0dt03408h

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Presentation] 特異な構造を持つ不飽和ケイ素化合物の化学2023

    • Author(s)
      岩本武明
    • Organizer
      広島大学講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Stable Silicon Analogues of Bicyclo[1.1.0]but-1(3)-ene and Their Derivatives2023

    • Author(s)
      Takeaki Iwamoto
    • Organizer
      Interplay of p-Block and Organometallic Chemistry
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 反転した立体配置のGe=Ge結合をもつ安定化合物の合成研究2023

    • Author(s)
      塩島 拓朗、岩本 武明
    • Organizer
      日本化学会第103春季年会2023
    • Related Report
      2022 Research-status Report
  • [Presentation] 低配位有機ケイ素化学種の構造有機化学2022

    • Author(s)
      岩本武明
    • Organizer
      第33回万有仙台シンポジウム
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] Stable Silicon Analogues of Bicyclo[1.1.0]but-1(3)-ene and Its Derivatives2022

    • Author(s)
      Takeaki Iwamoto
    • Organizer
      The 25th IUPAC International Conference on Physical Organic Chemistry
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Stable Bicyclic Silicon Compounds with a Nonclassical Structure2022

    • Author(s)
      Takeaki Iwamoto
    • Organizer
      International Main Group Element Chemistry Seminar 2022
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] 反転した立体配置の Ge=Ge 結合をもつ化合物の合成研究2022

    • Author(s)
      塩島 拓朗、岩本武明
    • Organizer
      第26回ケイ素化学協会シンポジウム
    • Related Report
      2022 Research-status Report
  • [Presentation] 安定性と反応性をもつ単離可能な低配位ケイ素化合物2022

    • Author(s)
      岩本武明
    • Organizer
      日本化学会第102春季年会2022
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] 嵩高いアルキル置換基を持つ低配位ケイ素化学種の合成、構造と反応2021

    • Author(s)
      岩本武明
    • Organizer
      第53回有機金属若手の会夏の学校
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] Highly Strained Bicyclic Disilenes and Related Species2021

    • Author(s)
      Takeaki Iwamoto
    • Organizer
      The 19th International Symposium on Silicon Chemistry
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] ケイ素-ケイ素π単結合を組み込んだπ共役系化合物の合成2021

    • Author(s)
      糠澤拓実、岩本武明
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] 2,4-ジアミノテトラシラビシクロ[1.1.0]ブト-1(3)-エンの構造と電子状態2021

    • Author(s)
      小池太智、岩本武明
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] 3 電子2中心Si-Si結合を有する化合物の構造と電子状態2021

    • Author(s)
      大澤來稀、小池太智、岩本武明
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] 反転 Si=Si 結合を持つジシレンのヒドリドとの反応2021

    • Author(s)
      糠澤拓実、岩本武明
    • Organizer
      第25回ケイ素化学協会シンポジウム
    • Related Report
      2021 Research-status Report
  • [Presentation] 反転Si=Si結合を持つジシレンと求核試薬の反応2021

    • Author(s)
      糠澤拓実、岩本武明
    • Organizer
      日本化学会第101春季年会(2021)
    • Related Report
      2020 Research-status Report
  • [Presentation] π型単結合を持つ新規ビシクロ[1.1.0]テトラシランの合成とその異性化反応2020

    • Author(s)
      糠澤拓実、岩本武明
    • Organizer
      基礎有機化学会 若手オンラインシンポジウム
    • Related Report
      2020 Research-status Report

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Published: 2020-08-03   Modified: 2025-01-30  

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