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Development of dinitrogen activation and ammonia synthesis by high-valence metal complexes

Research Project

Project/Area Number 16K05734
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionAichi Institute of Technology

Principal Investigator

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

Project Period (FY) 2016-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2019: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2018: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2017: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2016: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords窒素固定 / 窒素錯体 / 窒素活性化 / バナジウム / クロム / 二核錯体 / 金属錯体 / 高原子価 / トリアミドアミン / 生体機能利用 / モデル化 / アンモニア
Outline of Final Research Achievements

In this study, we succeeded to synthesize high-valent vanadium-, and chromium-dinitrogen complexes. When vanadium-dinitrogen complexes reacted with H+ in the presence of a reductant, only ammonia has formed, however, only hydrazine or hydrazine and ammonia have formed in case of chromium-dinitrogen complexes. We could not synthesize a nitride complex from the N-N bond cleavage of bridging N2 ligand in their dinitrogen complexes, however, we found that the yield of ammonia increases with preventing the decomposition of a dinitrogen complex in redox reactions. Particularly, we succeeded to improve the yield of ammonia to about 350% in case of vanadium-dinitrogen complex with 4-a methylbenzyl group. And when a vanadium-dinitrogen complex reacts with sodium or potassium, a alkali metal ion adduct forms without cleavage of a M-NN2 or a N-N bond, however, when using a chromium-dinitrogen complex, form a alkali metal ion adduct with cleavage of Cr-NN2 bond.

Academic Significance and Societal Importance of the Research Achievements

本研究において、高原子価窒素錯体の合成に成功したことは、窒素錯体の前駆体に高いポテンシャルを与えなくても遷移金属錯体上で窒素を活性化させることが可能であることを示している。このことは人工窒素固定法では必ずしも高温高圧を必要としないことを示しており、学術的意義は大変高い。また、窒素錯体を還元剤と反応させることによって、窒素配位子と中心金属の結合を優先的に切断できることは、窒素の選択的回収や除去に利用することができ、社会的意義も大きい。

Report

(5 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (13 results)

All 2020 2019 2018 2017 2016

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 3 results) Presentation (10 results) (of which Int'l Joint Research: 1 results)

  • [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
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Syntheses, characterizations, and crystal Structures of dinitrogen-divanadium complexes bearing triamidoamine ligands.2020

    • Author(s)
      Kokubo, Y., Wasada-Tsutsui, Y., Yomura, S., Yanagisawa, S., Kubo, M., Kugimiya, S., Kajita, Y., Ozawa, T., Masuda, H.
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2020 Issue: 15-16 Pages: 1456-1464

    • DOI

      10.1002/ejic.201901123

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Dinitrogen Fixation by Vanadium Complexes with a Triamidoamine Ligand2018

    • Author(s)
      Y. Kokubo, C. Yamamoto, K. Tsuzuki, T. Nagai, A. Katayama, T. Ohta, T. Ogura, Y. Wasada-Tsutsui, Y. Kajita, S. Kugimiya, H. Masuda
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 19 Pages: 11884-11894

    • DOI

      10.1021/acs.inorgchem.8b00982

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] トリアミドアミン配位子を用いた二核クロム(III)窒素錯体の合成と構造2020

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] トリアミドアミン配位子を有するクロム-窒素錯体の合成と構造2019

    • Author(s)
      山本千晶、梶田裕二
    • Organizer
      錯体化学会第69回討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 電子的特性の異なる置換基を有するトリアミドアミン配位子を用いた窒素錯体の合成と反応性2019

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      錯体化学会第69回討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] he Structures of Divanadium Dinitrogen Complexes Having a Triamidoamine2019

    • Author(s)
      Yoshiaki Kokubo, Kazuki Tsuzuki, Yuji Kajita
    • Organizer
      第29回 金属の関与する生体関連反応シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] The Reactivity of Divanadium Dinitrogen Complexes having Triamidoamine Ligand2019

    • Author(s)
      小久保佳亮、梶田裕二
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2019 Annual Research Report 2018 Research-status Report
  • [Presentation] Syntheses and Crystal Structures of Divanadium Dinitrogen Complexes2018

    • Author(s)
      Yoshiaki Kokubo, Kazuki Tsuzuki, Yuji Kajita
    • Organizer
      ICCC2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] トリアミドアミンと架橋窒素を配位子とする二核バナジウム錯体の結晶構造と電子的性質2018

    • Author(s)
      小久保佳亮、都築和貴、梶田裕二
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 二核バナジウム-窒素錯体における架橋窒素のプロトン化2017

    • Author(s)
      都築和貴、梶田裕二
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 窒素活性化を目的としたトリアミドアミン配位子を有するバナジウム錯体の合成2017

    • Author(s)
      都築和貴、梶田裕二
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 二核バナジウム-窒素錯体における窒素活性化挙動2016

    • Author(s)
      都築和貴、梶田裕二
    • 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

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Published: 2016-04-21   Modified: 2021-02-19  

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