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Synthesis of bifunctional complexes consisting of alkali and transition metals

Research Project

Project/Area Number 18H01992
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionTokyo Institute of Technology

Principal Investigator

Kawaguchi Hiiroyuki  東京工業大学, 理学院, 教授 (20262850)

Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2021: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2018: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Keywords多核錯体 / 遷移元素 / アルカリ金属 / フェノキシド錯体 / 遷移金属錯体 / 対イオン効果 / フェノキシド配位子 / 遷移金属 / 配位化学 / 小分子活性化 / 錯体化学 / 多座配位子
Outline of Final Research Achievements

Here we studied the synthesis of multinuclear complexes consisting of both transition metal ions as an electron-rich redox-active center and alkali metal ions as a Lewis acid. Such complexes can act as a bifunctional system capable of strongly polarizing substrates, thereby achieving activation small molecules such as dinitrogen and carbon dioxide. For example, the Ti-K complex prepared by the reaction of the titanium precursor with a potassium reagent is found to promote the coupling of dinitrogen and carbon dioxide via N-C bond formation, yielding hydrazide derivatives.

Academic Significance and Societal Importance of the Research Achievements

多様な酸化状態をとることができる遷移金属イオンとルイス酸として作用するアルカリ金属イオンを分子内で近傍に配置した多核金属錯体が、窒素分子のような反応性の低い物質の活性化に効果的に働くことを本研究で明らかにした。アルカリ金属イオンや溶媒を適切に選択することにより、そのルイス酸としての性質を系統的に変化させることができる。これにより、多核錯体の化学特性を制御することが可能であり、多様な分子変換を実現することが期待でき、学術的に興味深い。

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (19 results)

All 2022 2021 2020 2019 2018

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (14 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results)

  • [Journal Article] Systematic reductive oligomerization of isocyanides with a vanadium(ii) complex2021

    • Author(s)
      Hasegawa Sui、Ishida Yutaka、Kawaguchi Hiroyuki
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 67 Pages: 8296-8299

    • DOI

      10.1039/d1cc03463d

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Counterion Dependence of Dinitrogen Activation and Functionalization by a Diniobium Hydride Anion2020

    • Author(s)
      Suzuki Shoi、Ishida Yutaka、Kameo Hajime、Sakaki Shigeyoshi、Kawaguchi Hiroyuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 32 Pages: 13444-13450

    • DOI

      10.1002/anie.202006039

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and structures of titanium complexes bearing tetradentate tripodal [O2XC] ligands (X = C, P)2020

    • Author(s)
      Yusuke Nakanishi, Yutaka Ishida, Hiroyuki Kawaguchi
    • Journal Title

      Dalton Trans.

      Volume: 49 Issue: 1 Pages: 27-30

    • DOI

      10.1039/c9dt03969d

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dinitrogen Activation by a Heterometallic VFe Complex Derived from 1,1'‐Bis(arylamido)vanadocene2020

    • Author(s)
      Tsubasa Hatanaka, Hinano Kusunose, Hiroyuki Kawaguchi, Yasuhiro Funahashi
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2020 Issue: 15-16 Pages: 1449-1455

    • DOI

      10.1002/ejic.201901120

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] An anionic η2-naphthalene complex of titanium supported by a tripodal [O3C] ligand and its reactions with dinitrogen, anthracene and THF2018

    • Author(s)
      Nakanishi Yusuke、Ishida Yutaka、Kawaguchi Hiroyuki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 20 Pages: 6903-6907

    • DOI

      10.1039/c8dt01161c

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] フェノキシド配位子を持つ4族金属アレーン錯体の合成2022

    • Author(s)
      保坂 圭祐、石田 豊、川口 博之
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 架橋side-on end-on型窒素配位子を持つアニオン性ニオブ二核錯体の反応2022

    • Author(s)
      鈴木 直史、石田 豊、川口 博之
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] バナドセンおよびクロモセンビスアミド配位子を有する低原子価鉄およびコバルト錯体2022

    • Author(s)
      楠瀬 ひなの、畑中 翼、川口 博之、舩橋 靖博
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] メタロセン部位と金属間相互作用を持つビスアミド鉄およびコバルト錯体の合成と還元反応2021

    • Author(s)
      楠瀬 ひなの、畑中 翼、川口 博之、舩橋 靖博
    • Organizer
      錯体化学会第71回討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] アニオン性チタン窒素錯体とハロゲン化アルキルの反応2021

    • Author(s)
      貞金 輝久、中西 勇介、川口 博之、石田 豊
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] キレート型ビス(フェノキシド)配位子を用いたジルコニウムおよびハフニウム錯体の合成2021

    • Author(s)
      小島 拓、大口 真慧、石田 豊、川口 博之
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] バナドセンおよびクロモセンビスアミド部位を有する低原子価鉄およびコバルト錯体2021

    • Author(s)
      楠瀬 ひなの、畑中 翼、川口 博之、舩橋 靖博
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] アリールオキシド基を有するチタン窒素錯体の反応2019

    • Author(s)
      石田 豊, 中西 勇介, 長谷川 彗、川口博之
    • Organizer
      錯体化学討論会第69回
    • Related Report
      2019 Annual Research Report
  • [Presentation] バナドセンビスアミド配位子を有する鉄およびコバルト錯体の合成と還元反応2019

    • Author(s)
      楠瀬 ひなの, 畑中 翼, 川口 博之, 舩橋 靖博
    • Organizer
      錯体化学討論会第69回
    • Related Report
      2019 Annual Research Report
  • [Presentation] (ONO)型配位子を持つチタン錯体による窒素分子 活性化と官能基化反応2019

    • Author(s)
      石田 豊・長谷 川 彗・川口 博之
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] (ONO)型配位子を持つチタン錯体による窒素分子活性化2019

    • Author(s)
      石田豊・長谷川彗・川口博之
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 三座[OCO]型配位子を有するジルコニウム錯体の合成2019

    • Author(s)
      大口真慧・川口博之・石田豊
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Nitrogen-carbon bond formation by end-on bridging dinitrogen complexes of titanium2018

    • Author(s)
      Hiroyuki Kawaguchi
    • Organizer
      43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] P4 Activation by Early Transition Metal Hydride or Arene Complexes Bearing Aryloxide-Based Ligands2018

    • Author(s)
      Yutaka Ishida, Hiroyuki Kawaguchi
    • Organizer
      43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Annual Research Report

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Published: 2018-04-23   Modified: 2023-01-30  

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