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Synthesis of heterogeneous multinuclear highvalent dinitrogen complexes containing typical metal ions and development of electrochemical dinitrogen fixation method

Research Project

Project/Area Number 20K05545
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionAichi Institute of Technology

Principal Investigator

Yuji Kajita  愛知工業大学, 工学部, 教授 (60397495)

Project Period (FY) 2020-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2023: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2022: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2021: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords窒素固定 / 金属錯体触媒 / クロムイオン / バナジウムイオン / アルカリ金属イオン / トリアミドアミン配位子 / 窒素活性化 / 金属錯体 / バナジウム / クロム / アンモニア / 錯体触媒 / 典型金属イオン / 窒素錯体 / 異種多核 / 電気化学
Outline of Research at the Start

本研究では、環境低負荷型電気化学的窒素固定法を実現するため、窒素の過電圧を低下させることができ、配位した窒素上へ負電荷を誘起することができるとともに、高い触媒耐久性と副生する水素の抑制も期待できる生物模倣型金属錯体触媒の開発を行う。具体的には、中心金属周りを嵩高い置換基で覆うことができ、かつ、典型金属イオンを含有する異種多核高原子価窒素錯体を合成する。また、それを用いた電気化学的窒素固定法を開発し、環境低負荷型電気化学的窒素固定法の実現に向けた課題を明確にする。

Outline of Final Research Achievements

In this time, we succeeded in synthesizing vanadium- and chromium-dinitrogen complexes with many alkali metal ions added by reacting triamidoamine derivatives with vanadium(III) and chromium(III). We succeeded in determining the crystal structures of all the successfully synthesized complexes. Furthermore, regarding the activation of bridged dinitrogen ligands, we found that bridges between multiple transition metal ions can donate more electrons to the bridged dinitrogen ligands, resulting in more activation. Furthermore, regarding the activation effects of sodium ions and potassium ions on the dinitrogen ligand in the complex that was successfully synthesized, it was revealed that potassium ions can activate the dinitrogen ligand to a greater extent.

Academic Significance and Societal Importance of the Research Achievements

今回我々の研究は、低い過電圧で窒素分子を還元できる金属錯体触媒の開発を目標とし、その目標に向けて、多くの新規異種多核金属錯体を合成し、それらの構造を決定した。これらの結果は、高原子価を有する窒素活性化錯体として大変貴重な例であり、学術的な価値が大変高いと考えられる。また、安価なアルカリ金属イオンを付加させることによりさらなる二窒素配位子の活性化に成功させることができ、かつカリウムイオンの方がナトリウムイオンよりも活性化能が高いという結果を得たことは、新規の窒素固定法を開発する上で工業的、社会的にも大変価値があると考えられる。

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

    (15 results)

All 2024 2023 2022 2021 2020

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 2 results) Presentation (12 results) (of which Int'l Joint Research: 3 results)

  • [Journal Article] yntheses, Characterizations, Crystal Structures, and Protonation Reactions of Dinitrogen Chromium Complexes Supported with Triamidoamine Ligands2023

    • Author(s)
      Yoshiaki Kokubo, Kazuki Tsuzuki, Hikari Sugiura, Chiaki Yamamoto, Shunsuke Yomura, Yuko Wasada-Tsutsui, Tomohiro Ozawa, Sachiko Yanagisawa, Minoru Kubo, Shinichi Kugimiya, Hideki Masuda, and Yuji Kajita
    • Journal Title

      Inorg. Chem.

      Volume: 62 Issue: 14 Pages: 5320-5333

    • DOI

      10.1021/acs.inorgchem.2c01561

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] The Steric Effect in Preparations of Vanadium(II)/(III) Dinitrogen Complexes of Triamidoamine Ligands Bearing Bulky Substituents2022

    • Author(s)
      Kokubo Yoshiaki、Igarashi Itsuki、Nakao Kenichi、Hachiya Wataru、Kugimiya Shinichi、Ozawa Tomohiro、Masuda Hideki、Kajita Yuji
    • Journal Title

      Molecules

      Volume: 27 Issue: 18 Pages: 5864-5864

    • DOI

      10.3390/molecules27185864

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Efficient Electronic Structure to Stabilize N2‐Bridged Dinuclear Complexes Intended for N2 Activation: Iminophosphorane Iron(I) and Cobalt(I)2020

    • Author(s)
      Yuko Wasada-Tsutsui, Hiroaki Wasada, Tatsuya Suzuki, Akira Katayama, Yuji Kajita, Tomohiko Inomata, Tomohiro Ozawa, and Hideki Masuda
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 15-16 Issue: 15-16 Pages: 1411-1417

    • DOI

      10.1002/ejic.201901131

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] バナジウムおよびクロムを用いた異種二核窒素錯体の構造と反応性2024

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      日本化学会第104春季年会
    • Related Report
      2023 Annual Research Report
  • [Presentation] かさ高い置換基を持つトリアミドアミン配位子を用いたクロム窒素錯体の合成と構造2023

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      錯体化学会第73回討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 末端N原子に第三級炭素が隣接しているトリアミドアミン配位子を用いたクロム窒素錯体の合成と構造2023

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] Syntheses and Structures of Vanadium Dinitrogen Complexes Supported with Triamidoamine Ligand with a Series of Sterically Hindered Substituents2022

    • Author(s)
      Yoshiaki Kokubo, Yuji Kajita
    • Organizer
      8th Asian Conference on Coordination Chemistry
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Syntheses and Structures of Vanadium Dinitrogen Complexes Bearing Triamidoamine Ligands with Alkali Ions2022

    • Author(s)
      Yoshiaki Kokubo, Yuji Kajita
    • Organizer
      錯体化学会第72回討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] トリアミドアミン配位子の末端N原子に第三級炭素が隣接したバナジウム窒素錯体の合成と構造2022

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      第53回中部化学関係学協会支部連合秋季大会
    • Related Report
      2022 Research-status Report
  • [Presentation] The Syntheses and Structures of Dinitrogen Chromium Complexes Supported with Triamidoamine Ligands2022

    • Author(s)
      小久保佳亮、梶田裕二、増田秀樹
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] The Effect of Bulkier Substituents to Vanadium Dinitrogen Complexes bearing Triamidoamine Ligands2021

    • Author(s)
      Yoshiaki Kokubo, Yuji Kajita
    • Organizer
      錯体化学会第71回討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] Syntheses and protonation reactivity of dinitrogen-divanadium complexes bearing a series of triamidoamine ligands2021

    • Author(s)
      Yoshiaki Kokubo, Yuji Kajita
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Syntheses, characteriozations, and reactivities of dinitrogen-dichromium complexes bearing triamidoamine ligands2021

    • Author(s)
      Tomomi Isogai, Yoshiaki Kokubo, Yuji Kajita
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] かさ高い置換基を持つトリアミドアミン配位子を用いたバナジウム窒素錯体の合成と構造2021

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] 三級炭素原子が末端N原子に隣接したトリアミドアミン配位子を持つバナジウム錯体の合成と構造2020

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      錯体化学会第70回討論会
    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2025-01-30  

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