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Development of catalytic nitrogen fixation by first transition metal complexes bearing hard-soft ligands

Research Project

Project/Area Number 19K23645
Research Category

Grant-in-Aid for Research Activity Start-up

Allocation TypeMulti-year Fund
Review Section 0502:Inorganic/coordination chemistry, analytical chemistry, inorganic materials chemistry, energy-related chemistry, and related fields
Research InstitutionThe University of Tokyo

Principal Investigator

Kuriyama Shogo  東京大学, 大学院工学系研究科(工学部), 助教 (50850723)

Project Period (FY) 2019-08-30 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords窒素固定 / 鉄 / ロジウム / イリジウム / ピンサー配位子 / シリルアミン / 遷移金属窒素錯体 / 第一遷移金属 / ハード・ソフト配位子
Outline of Research at the Start

遷移金属錯体を用いた温和な条件下での触媒的窒素固定反応の成功例は限られている。そこで、高原子化状態を安定化するハードなドナーと低原子価状態を安定化するソフトなドナーを組み合わせたピンサー配位子が触媒的窒素固定反応に有効であると着想した。
本研究では対応するピンサー配位子を持つ鉄・コバルト・マンガン・クロムといった第一遷移金属窒素錯体の合成と達成例のないこれら金属錯体を用いた常温・常圧での窒素分子からの触媒的アンモニア生成反応の開発を目指す。

Outline of Final Research Achievements

In this research, transition metal-dinitrogen complexes with pincer ligands bearing both a hard donor and a soft donor were synthesized to develop the catalytic nitrogen fixation under mild reaction conditions. As a result, it was found that an iron complex having an anionic PCP-type pincer ligand worked as a highly active catalyst for the reduction of dinitrogen into ammonia and hydrazine. Also, rhodium- and iridium-catalyzed formation of silylamine from dinitrogen was developed by using a rhodium complex having an anionic PNP-type pincer ligand and an iridium complex having an anionic PCP-type pincer ligand as catalysts, respectively.

Academic Significance and Societal Importance of the Research Achievements

本研究で開発した鉄錯体は、窒素分子からの触媒的アンモニア・ヒドラジン生成反応に対してこれまで報告されている他の鉄錯体を超える触媒活性を有することを見出した。また、ロジウム・イリジウム錯体による触媒的シリルアミン生成反応は、ロジウム・イリジウム触媒による窒素固定反応の世界初の例である。本研究で得られた成果は、遷移金属錯体による温和な条件下における触媒的窒素固定反応に対して新たな知見を与えるものである。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (26 results)

All 2021 2020 2019 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Open Access: 1 results) Presentation (16 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results) Remarks (2 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Synthesis and Characterization of Rhodium Complex Bearing Anionic CNC‐Type Pincer Ligand with Pyrrolide and Imidazo[1,5‐ a ]pyridin‐3‐ylidene Moieties2021

    • Author(s)
      Kuriyama Shogo、Zhao Wenhao、Nishibayashi Yoshiaki
    • Journal Title

      Zeitschrift fur anorganische und allgemeine Chemie

      Volume: - Issue: 14 Pages: 1-8

    • DOI

      10.1002/zaac.202100065

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of catalytic nitrogen fixation using transition metal complexes not relevant to nitrogenases2021

    • Author(s)
      Kuriyama Shogo、Nishibayashi Yoshiaki
    • Journal Title

      Tetrahedron

      Volume: 83 Pages: 131986-131986

    • DOI

      10.1016/j.tet.2021.131986

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iridium-catalyzed Formation of Silylamine from Dinitrogen under Ambient Reaction Conditions2020

    • Author(s)
      Kawakami Ryosuke、Kuriyama Shogo、Tanaka Hiromasa、Konomi Asuka、Yoshizawa Kazunari、Nishibayashi Yoshiaki
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 7 Pages: 794-797

    • DOI

      10.1246/cl.200254

    • NAID

      130007872579

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ruthenium-Catalyzed Propargylic Reduction of Propargylic Alcohols with Hantzsch Ester2020

    • Author(s)
      Haowei Ding, Ken Sakata, Shogo Kuriyama, and Yoshiaki Nishibayashi
    • Journal Title

      Organometallics

      Volume: 39 Issue: 11 Pages: 2130-2134

    • DOI

      10.1021/acs.organomet.0c00187

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation and reactivity of molybdenum complexes bearing pyrrole-based PNP-type pincer ligand2020

    • Author(s)
      Tanabe Yoshiaki、Sekiguchi Yoshiya、Tanaka Hiromasa、Konomi Asuka、Yoshizawa Kazunari、Kuriyama Shogo、Nishibayashi Yoshiaki
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 51 Pages: 6933-6936

    • DOI

      10.1039/d0cc02852e

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic reduction of dinitrogen to tris(trimethylsilyl)amine using rhodium complexes with a pyrrole-based PNP-type pincer ligand2019

    • Author(s)
      Kawakami Ryosuke、Kuriyama Shogo、Tanaka Hiromasa、Arashiba Kazuya、Konomi Asuka、Nakajima Kazunari、Yoshizawa Kazunari、Nishibayashi Yoshiaki
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 99 Pages: 14886-14889

    • DOI

      10.1039/c9cc06896a

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] アニオン性 PCP型ピンサー配位子を有する鉄窒素錯体を用いた触媒的窒素固定反応2021

    • Author(s)
      栗山翔吾、加藤孟、田中宏昌、許斐明日香、吉澤一成、西林仁昭
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Mechanistic Study on Rhenium-Catalyzed Ammonia Formation from Dinitrogen under Mild Reaction Conditions2021

    • Author(s)
      MENG, Fanqiang; KURIYAMA, Shogo; TANAKA, Hiromasa; EGI, Akihito; YOSHIZAWA, Kazunari; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Reactivity of Cobalt Dinitrogen Complexes Bearing Anionic PCP-type Pincer Ligands toward Nitrogen Fixation2021

    • Author(s)
      WEI, Shenglan; KURIYAMA, Shogo; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Ruthenium-Catalyzed Enantioselective Propargylic Reduction of Propargylic Alcohols with Hantzsch Esters2021

    • Author(s)
      DING, Haowei; KURIYAMA, Shogo; SAKATA, Ken; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Development of C-N Bond Formation Reactions from Molybdenum-Nitride Complex with Carbon Centered Electrophiles Directed toward Formation of Organonitrogen Compounds2021

    • Author(s)
      ITABASHI, Takayuki; ARASHIBA, Kazuya; KURIYAMA, Shogo; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Catalytic Cycloaddition Reactions between Propargylic Alcohols Derivatives and Hydrazones2021

    • Author(s)
      LIU, Shiyao; TANABE, Yoshiaki; KURIYAMA, Shogo; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] モリブデン錯体を用いた触媒的アンモニア合成反応における PNP型ピンサー配位子上の置換基効果2021

    • Author(s)
      光本泰知, 芦田裕也, 荒芝和也, 栗山翔吾, 西林仁昭
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Catalytic Ammonia Formation by Dinitrogen Bridged Dirhenium Complex Bearing PNP Pincer Ligands under Mild Reaction Conditions2020

    • Author(s)
      MENG, Fanqiang; KURIYAMA, Shogo; TANAKA, Hiromasa; EGI, Akihito; YOSHIZAWA, Kazunari; NISHIBAYASHI, Yoshiaki
    • Organizer
      錯体化学会第70回討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] PNP型ピンサー配位子を有するモリブデン触媒を用いた水をプロトン源とした触媒的アンモニア合成反応における置換基効果2020

    • Author(s)
      光本泰知, 芦田裕也, 荒芝和也, 栗山翔吾, 中島一成, 西林仁昭
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] ピロール骨格PNP型ピンサー配位子を有するモリブデン錯体の合成と反応性2020

    • Author(s)
      田辺資明, 関口義也, 栗山翔吾, 中島一成, 西林仁昭
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Catalytic Nitrogen Fixation Using Rhenium-Dinitrogen Complexes Bearing PNP Pincer Ligands2020

    • Author(s)
      MENG, Fanqiang; KURIYAMA, Shogo; NAKAJIMA, Kazunari; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Synthesis and Reactivity of Manganese Complexes Bearing Anionic Pincer Ligands toward Nitrogen Fixation2020

    • Author(s)
      WEI, Shenglan; KURIYAMA, Shogo; NAKAJIMA, Kazunari; NISHIBAYASHI, Yoshiaki
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] PNP型ピンサー配位子を有するロジウム窒素錯体を用いた触媒的窒素固定反応2019

    • Author(s)
      川上亮祐、栗山翔吾、中島一成、西林仁昭
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] PNP 型ピンサー配位子を有するロジウム窒素錯体を用いた窒素分子の触媒的シリル化反応2019

    • Author(s)
      川上亮祐, 荒芝和也, 栗山翔吾, 中島一成, 西林仁昭
    • Organizer
      第23回ケイ素化学協会シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] Catalytic Reduction of Dinitrogen to Ammonia and N(SiMe3)3 Using Rhenium Complexes2019

    • Author(s)
      Fanqiang Meng, Shogo Kuriyama, Kazunari Nakajima, Yoshiaki Nishibayashi
    • Organizer
      4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] アンモニアのエネルギーキャリア利用を志向した温和な条件下での触媒的窒素固定反応の開発2019

    • Author(s)
      栗山翔吾
    • Organizer
      エネルギー研究クラスター/第 1 回若手研究会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Remarks] 西林 研究室|東京大学大学院工学系研究科

    • URL

      http://park.itc.u-tokyo.ac.jp/nishiba/

    • Related Report
      2020 Annual Research Report
  • [Remarks] 西林研究室|東京大学大学院工学研究科システム創成学専攻エネルギー資源創成

    • URL

      http://webpark1495.sakura.ne.jp/index.html

    • Related Report
      2019 Research-status Report
  • [Patent(Industrial Property Rights)] 鉄錯体及び鉄ハロゲン錯体並びにアンモニア及びヒドラジンの製造方法2020

    • Inventor(s)
      西林仁昭、栗山翔吾、近藤章一、菊池隆正
    • Industrial Property Rights Holder
      西林仁昭、栗山翔吾、近藤章一、菊池隆正
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2019 Research-status Report
  • [Patent(Industrial Property Rights)] アンモニア及びヒドラジンの製造方法、並びに該製造方法に用いる鉄触媒及びその製造方法2020

    • Inventor(s)
      西林仁昭、栗山翔吾、近藤章一、菊池隆正
    • Industrial Property Rights Holder
      西林仁昭、栗山翔吾、近藤章一、菊池隆正
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2019 Research-status Report

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Published: 2019-09-03   Modified: 2022-01-27  

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