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Properties of Organometallic Complexes Derived from CH Bond Activation of Calixarenes

Research Project

Project/Area Number 15K05460
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionChuo University

Principal Investigator

Ishii Youichi  中央大学, 理工学部, 教授 (40193263)

Co-Investigator(Kenkyū-buntansha) 小玉 晋太朗  中央大学, 理工学部, 助教 (30612189)
Co-Investigator(Renkei-kenkyūsha) TAKANO Keiko  お茶の水女子大学, 大学院人間文化創成科学研究科, 教授 (00143701)
Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsカリックスアレーン / イリジウム / ロジウム / CH結合活性化 / Cp*配位子 / ハプテシティ変化 / πアリル錯体 / カルベン錯体 / N-ヘテロサイクリックカルベン / C-H結合活性化 / ピラーアレーン / ハプティシティ変化 / 配位子置換 / イソシアニド
Outline of Final Research Achievements

The first examples of (kappa)3-O,C,O tridentate calix[4]arene transition metal complexes [Cp*Ir{(C6H2tBu)4(CH)(CH2)3(O)(OH)3}] (M = Ir, Rh) that are stable both in the solid state and in solution were synthesized. The reaction of the Ir complex with 2 equiv of xylyl isocyanide afforded the ((eta)1-Cp*)Ir(CNXy)2 complex in which the Cp* ligand is slipped from an (eta)5- to an (eta)1-fashion, although ring slippage of (eta)5-Cp* ligand is by far uncommon compared with that of Cp. The reaction of the ((eta)1-Cp*)Ir complex with additional 1 equiv of isocyanide resulted in the liberation of the Cp* ligand as Cp*H, which is confirmed by 1H NMR. This study provides the first observation of stepwise dissociation of Cp* ligand from group 4-10 transition metals via (eta)1-coordination. This unique phenomenon seems to be facilitated by flexible coordination of an OH group in the C-metallated calix[4]arene ligand.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (6 results)

All 2018 2017 2016

All Presentation (6 results) (of which Int'l Joint Research: 2 results)

  • [Presentation] Stepwise Dissociation of Pentamethylcyclopentadienyl Ligand in an (η5-Cp*)Ir Complex with a κ3-O,C,O Tridentate Calix[4]arene Ligand2018

    • Author(s)
      Takuya Kuwabara, Ryogen Tezuka, Mikiya Ishikawa, Takuya Yamazaki, Shintaro Kodama, Youichi Ishii
    • Organizer
      XXVIII International Conference on Organometallic Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of a Calix[8]arene Complex with a Diiridium Core inside the Cavity through Double CH Activation2018

    • Author(s)
      Takuya Toriumi, Takuya Kuwabara, Shintaro Kodama, Youichi Ishii
    • Organizer
      XXVIII International Conference on Organometallic Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] カリックスアレーンのCH活性化を利用したCp*Rh(III)錯体の合成2017

    • Author(s)
      手塚良玄、石川幹也、小玉晋太朗、石井洋一
    • Organizer
      日本化学会第97回春季年会
    • Place of Presentation
      慶応義塾大学
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] CH活性化されたカリックスアレーンを三座配位子として含むCp*Rh(III) 錯体2017

    • Author(s)
      手塚良玄、石川幹也、桑原拓也、小玉晋太朗、石井洋一
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ピラー[5]アレーンを配位子とした8, 9族金属錯体の合成と性質2016

    • Author(s)
      近藤潤、佐伯真由美、小玉晋太朗、石井洋一
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] Pillar[5]arene を配位子とした 9 属金属錯体の合成と性質2016

    • Author(s)
      近藤潤、佐伯真由美、小玉晋太朗、石井洋一
    • Organizer
      日本化学会第 96 春季年会
    • Place of Presentation
      同支社大学京田辺キャンパス
    • Year and Date
      2016-03-25
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2019-03-29  

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