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

骨格構成元素として高周期14族元素を含むアリールアニオン種の合成とその性質解明

Research Project

Project/Area Number 16J09198
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field Organic chemistry
Research InstitutionKyoto University

Principal Investigator

藤森 詩織  京都大学, 理学研究科, 特別研究員(DC1)

Project Period (FY) 2016-04-22 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2018: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2017: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2016: ¥700,000 (Direct Cost: ¥700,000)
Keywords高周期14族元素 / 芳香族化合物 / フェニルアニオン / ゲルマニウム / スズ / 錯体 / ケイ素 / 高周期14族元素
Outline of Annual Research Achievements

これまでの研究からベンゼン骨格を有する「重いフェニルアニオン」は、環状共役構造とともに二価化学種としての性質を有することを明らかとした。そこで次に、ベンゼン骨格の系よりも共役が広がることにより、二価化学種としての性質が強く発現することが予想されるアントラセン骨格での検討を行った。ゲルマニウム上にかさ高いアリール基(Ar)を有する重いアントラセンに対し、還元剤を作用させることにより、重いアンスリルアニオンの三量体であるトリアニオンが得られた。X線結晶構造解析および理論計算の結果から、得られたトリアニオンは、一分子に「1つのゲルミルアニオン」と「2つの非局在化アニオン」という異なる二種類のアニオンを含んだユニークな形式のトリアニオンであることが明らかとなった。このトリアニオンの生成は、中間体として重いアンスリルアニオンが発生していることを示唆しており、ベンゼン骨格からアントラセン骨格へ共役が広がったことにより二価化学種としての性質がより強く発現した結果、三量体であるトリアニオンが得られたものと考えている。この結果は、アニオン種の性質をチューニングすることに成功したことを示唆しており、重要な成果である。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Report

(3 results)
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (23 results)

All 2019 2018 2017 2016 Other

All Journal Article (7 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 7 results,  Open Access: 2 results,  Acknowledgement Compliant: 1 results) Presentation (14 results) (of which Int'l Joint Research: 7 results,  Invited: 1 results) Remarks (2 results)

  • [Journal Article] A Mixed-Anion System Consisting of a Germyl Anion and Anions Delocalized on Conjugated Carbon Ring Skeletons2019

    • Author(s)
      Fujimori Shiori、Mizuhata Yoshiyuki、Tokitoh Norihiro
    • Journal Title

      Chemistry - A European Journal

      Volume: 25 Issue: 25 Pages: 6284-6289

    • DOI

      10.1002/chem.201900699

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ru-Complexes of an anionic germabenzenyl ligand2018

    • Author(s)
      Fujimori Shiori、Mizuhata Yoshiyuki、Tokitoh Norihiro
    • Journal Title

      Chemical Communications

      Volume: 54 Issue: 58 Pages: 8044-8047

    • DOI

      10.1039/c8cc02845a

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Neutral, Cationic and Hydride-substituted Siloxygermylenes2018

    • Author(s)
      Roy Matthew M. D.、Fujimori Shiori、Ferguson Michael J.、McDonald Robert、Tokitoh Norihiro、Rivard Eric
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 54 Pages: 14392-14399

    • DOI

      10.1002/chem.201802958

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Generation of stannabenzenes and their monomer?dimer equilibration2018

    • Author(s)
      Mizuhata Yoshiyuki、Fujimori Shiori、Noda Naoya、Kanesato Shuhei、Tokitoh Norihiro
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 41 Pages: 14436-14444

    • DOI

      10.1039/c8dt02994f

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stannabenzenylpotassium: The First Isolable Tin‐Containing Benzene Derivative2018

    • Author(s)
      Fujimori Shiori、Mizuhata Yoshiyuki、Tokitoh Norihiro
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 64 Pages: 17039-17045

    • DOI

      10.1002/chem.201804858

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Heavy Phenyllithium and -sodium: Synthesis and Characterization of Germanium Analogues of Phenyl Anion (‘Germabenzenyl Anions’)2018

    • Author(s)
      Shiori Fujimori, Yoshiyuki Mizuhata, Norihiro Tokitoh
    • Journal Title

      Chemistry Letters

      Volume: 印刷中 Issue: 6 Pages: 708-710

    • DOI

      10.1246/cl.180170

    • NAID

      130007384497

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Germabenzenylpotassium: A Germanium Analogue of a Phenyl Anion2017

    • Author(s)
      Mizuhata, Y.; Fujimori, S.; Sasamori, T.; Tokitoh, N.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 56 Issue: 16 Pages: 4588-4592

    • DOI

      10.1002/anie.201700801

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] 含高周期14族元素アリールアニオン種の合成と性質2018

    • Author(s)
      ○藤森詩織、水畑吉行、時任宣博
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Synthesis, Structure, and Reactivity of Germa- and Stannabenzenyl Anions2018

    • Author(s)
      ○Shiori Fujimori, Yoshiyuki Mizuhata, Norihiro Tokitoh
    • Organizer
      The 15th International Symposium on Inorganic Ring Systems (IRIS-15)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Structure of Heavier Group 14 Element Analogues of Aryl Anions2018

    • Author(s)
      ○Shiori Fujimori, Yoshiyuki Mizuhata, Norihiro Tokitoh
    • Organizer
      The 28th International Conference on Organometallic Chemistry (ICOMC 2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 含高周期14族元素ポリアニオンの合成と構造2018

    • Author(s)
      ○藤森詩織、水畑吉行、時任宣博
    • Organizer
      第22回ケイ素化学協会シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 含高周期14族元素アリールアニオン種の縮合多環芳香族骨格への拡張2018

    • Author(s)
      藤森詩織、水畑吉行、時任宣博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis and Structure of Heavier Group 14 Element Analogues of Aryl Anions2018

    • Author(s)
      Shiori Fujimori, Yoshiyuki Mizuhata, Norihiro Tokitoh
    • Organizer
      he 28th International Conference on Organometallic Chemistry (ICOMC-28)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Structure of Heavier Group 14 Analogues of Phenyl Anion2017

    • Author(s)
      ○Shiori Fujimori, Yoshiyuki Mizuhata, Takahiro Sasamori, Norihiro Tokitoh
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      東京都
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] Synthesis and Isolation of Stable Germabenzenyl Anions2017

    • Author(s)
      Norihiro Tokitoh, Shiori Fujimori, Yoshiyuki Mizuhata, Takahiro Sasamori
    • Organizer
      The 12th International Conference of Heteroatom Chemistry (ICHAC-12)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] フェニルアニオンの高周期14族元素類縁体の合成と性質2017

    • Author(s)
      藤森詩織、水畑吉行、時任宣博
    • Organizer
      第44回有機典型元素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ゲルマベンゼニルアニオンの合成と性質2016

    • Author(s)
      ○藤森詩織、水畑吉行、笹森貴裕、時任宣博
    • Organizer
      第20回ケイ素化学協会シンポジウム
    • Place of Presentation
      滋賀県
    • Year and Date
      2016-10-07
    • Related Report
      2016 Annual Research Report
  • [Presentation] Synthesis, Structure, and Reactivity of Germabenzenyl Anions2016

    • Author(s)
      ○Yoshiyuki Mizuhata, Shiori Fujimori, Shuhei Kanesato, Naoya Noda, Takahiro Sasamori, Norihiro Tokitoh
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      東京都
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] Structure and Reactivity of Germabenzenylpotassium2016

    • Author(s)
      Shiori Fujimori, Yoshiyuki Mizuhata, Takahiro Sasamori, ○Norihiro Tokitoh
    • Organizer
      15th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead
    • Place of Presentation
      Pardubice, Czech Republic
    • Year and Date
      2016-08-28
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and Properties of Germabenzenyl Anions2016

    • Author(s)
      ○Shiori Fujimori, Yoshiyuki Mizuhata, Takahiro Sasamori, Norihiro Tokitoh
    • Organizer
      15th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead
    • Place of Presentation
      Pardubice, Czech Republic
    • Year and Date
      2016-08-28
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Reaction of Germabenzenylpotassium with [Cp*RuCl]4: Unexpected Formation of Ruthenium-substituted Germabenzene2016

    • Author(s)
      ○Shiori Fujimori, Yoshiyuki Mizuhata, Takahiro Sasamori, Norihiro Tokitoh
    • Organizer
      The 27th International Conference on Organometallic Chemistry
    • Place of Presentation
      Melbourne Australia
    • Year and Date
      2016-07-17
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Remarks] 初めての安定なスズ核置換ベンゼン誘導体の合成

    • URL

      https://www.kuicr.kyoto-u.ac.jp/sites/topics/181207/

    • Related Report
      2018 Annual Research Report
  • [Remarks] 「重いフェニルアニオン」の錯体ビルディングブロックとしての活用

    • URL

      https://www.kuicr.kyoto-u.ac.jp/sites/topics/180803/

    • Related Report
      2018 Annual Research Report

URL: 

Published: 2016-05-17   Modified: 2024-03-26  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi