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Precise Formation of Dinuclear Organometallic Reaction Sites and their Application in Difficult Substrate Reductions

Publicly Offered Research

Project AreaPrecise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
Project/Area Number 18H04246
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Research InstitutionNagoya University

Principal Investigator

大木 靖弘  名古屋大学, 理学研究科, 准教授 (10324394)

Project Period (FY) 2018-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Keywordsモリブデン / 鉄 / ヒドリド / 二核錯体 / 還元反応 / 窒素 / シリル化 / 有機金属錯体
Outline of Annual Research Achievements

自然界でN2を還元する酵素ニトロゲナーゼの活性中心FeMo-cofactorは、N2を取り込む活性状態で複数の架橋ヒドリドを持つと考えられている。令和元年度の本研究では、昨年度に合成したヒドリド架橋Mo-Fe二核錯体を触媒として用い、N2のシリル化反応を検討した。その結果、四つのヒドリドを持つ中性Mo-Fe二核錯体を触媒前駆体とした場合に129±20当量のN(SiMe3)3が生成した。この触媒火星は、現在までにMo触媒反応(~226当量)やFe触媒反応(~183当量)で報告されている最高値よりは低いものの、Mo, Fe触媒反応の中ではいずれも二番目に相当する。またMo-Fe二核錯体の触媒活性は、先行研究で用いた四核Mo2Fe2クラスター(69±7当量)と比較して、錯体あたり2倍弱、金属数あたり4倍弱に向上している。一方で、原料として用いたMo単核錯体やFe単核錯体は触媒活性を示さなかったことから、Mo-Fe二核錯体が単核Mo, Fe錯体へと分解して触媒活性種を生じる可能性は低いと考えられる。中性のMo-Fe錯体が良好な触媒活性を示したのに対して、ヒドリドを一つ抜いてカチオン性にしたMo-Fe二核錯体の触媒活性は著しく低下した。カチオン性錯体は触媒反応条件でNaにより還元され、続く配位子の不均化により触媒不活性な混合物を生じるためと考えている。カチオン性錯体とLiPPh2の反応から合成した、架橋ホスフィド配位子を持つMo-Fe二核錯体は、他のMo-Fe二核錯体より還元された状態であるため、N2の活性化に有利と予想したが、その触媒活性は上述した中性Mo-Fe二核錯体より低かった。かさ高いホスフィド配位子が金属周りを覆い、N2を近づき難くしていることが、低活性になった原因だと考えている。以上の結果と昨年度の結果を論文としてまとめ、Chem. Eur. J.誌にて発表した。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (21 results)

All 2020 2019 2018 Other

All Int'l Joint Research (2 results) Journal Article (10 results) (of which Int'l Joint Research: 7 results,  Peer Reviewed: 10 results,  Open Access: 1 results) Presentation (9 results) (of which Int'l Joint Research: 7 results,  Invited: 9 results)

  • [Int'l Joint Research] University of California, Irvine/University of Hawaii(米国)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] University of California, Irvine/University of Hawaii(米国)

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Synthesis of Dinuclear Mo‐Fe Hydride Complexes and Catalytic-Silylation of N22020

    • Author(s)
      Ishihara Kodai、Araki Yuna、Tada Mizuki、Takayama Tsutomu、Sakai Yoichi、Sameera W. M. C.、Ohki Yasuhiro
    • Journal Title

      Chemistry: A European Journal

      Volume: - Issue: 43 Pages: 9537-9546

    • DOI

      10.1002/chem.202000104

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Characterization, and Application of Segphos Derivative Having Diferrocenylphosphino-Donor Moieties2020

    • Author(s)
      Hao Hu, Hiroki Ichiryu, Naoki Seki, Kiyohiko Nakajima, Yasuhiro Ohki, Masamichi Ogasawara
    • Journal Title

      Organometallics

      Volume: 39 Issue: 6 Pages: 788-792

    • DOI

      10.1021/acs.organomet.9b00865

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of [Mo3S4] Clusters through Half-Sandwich Mo(V) Chlorides and Their Application as Platforms for [Mo3S4Fe] Cubes2019

    • Author(s)
      Yasuhiro Ohki, Ryota Hara, Kenichiro Munakata, Mizuki Tada, Tsutomu Takayma, Yoichi Sakai, Roger E. Cramer
    • Journal Title

      Inorg. Chem.

      Volume: 58 Issue: 8 Pages: 5230-5240

    • DOI

      10.1021/acs.inorgchem.9b00309

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Recent Advances in the Chemical Synthesis of Nitrogenase Model Clusters2019

    • Author(s)
      Kazuki Tanifuji, Yasuhiro Ohki
    • Journal Title

      Struct. Bond.

      Volume: 179 Pages: 33-61

    • DOI

      10.1007/430_2018_26

    • ISBN
      9783030258962, 9783030258979
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Chemical Synthesis of an Asymmetric Mo-Fe-S Mimic of Nitrogenase Active Site2019

    • Author(s)
      Kazuki Tanifuji, Yasuhiro Ohki
    • Journal Title

      Methods Mol. Biol.

      Volume: 1876 Pages: 229-244

    • DOI

      10.1007/978-1-4939-8864-8_15

    • ISBN
      9781493988631, 9781493988648
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 3-[4'-(Diethylboryl)phenyl]pyridine: Exclusive Crystallization of Cyclic Tetramer2019

    • Author(s)
      Shigeharu Wakabayashi, Natsu Sugiyama, Yasuhiro Ohki, Takahito Itoh, Toshikazu Kitagawa
    • Journal Title

      Chem. Asian J.

      Volume: 14 Issue: 4 Pages: 568-573

    • DOI

      10.1002/asia.201801698

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cubane-Type [Mo3S4M] Clusters with First-Row Group 4-10 Transition-Metal Halides Supported by C5Me5 Ligands on Molybdenum2018

    • Author(s)
      Yasuhiro Ohki, Keisuke Uchida, Ryota Hara, Mami Kachi, Mayu Fujisawa, Mizuki Tada, Yoichi Sakai, W. M. C. Sameera
    • Journal Title

      Chem. Eur. J.

      Volume: 24 Issue: 64 Pages: 17138-17147

    • DOI

      10.1002/chem.201804083

    • NAID

      120006577103

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] N2 Activation on a Molybdenum-Titanium-Sulfur Cluster2018

    • Author(s)
      Y. Ohki, K. Uchida, M. Tada, R. E. Cramer, T. Ogura, and T. Ohta
    • Journal Title

      Nature Communications

      Volume: 9 Issue: 1 Pages: 3200-3200

    • DOI

      10.1038/s41467-018-05630-6

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Ambient Conversion of CO2 to Hydrocarbons by Biogenic and Synthetic [Fe4S4] clusters2018

    • Author(s)
      Martin T. Stiebritz, Caleb J. Hiller, Nathaniel S. Sickerman, Chi Chung Lee, Kazuki Tanifuji, Yasuhiro Ohki, Yilin Hu
    • Journal Title

      Nature Catal.

      Volume: 1 Issue: 6 Pages: 444-451

    • DOI

      10.1038/s41929-018-0079-4

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Tracing the ‘Ninth Sulfur’ of the Nitrogenase Cofactor via a Semi-Synthetic Approach2018

    • Author(s)
      Kazuki Tanifuji, Chi Chung Lee, Kazuyuki Tatsumi, Yasuhiro Ohki, Yilin Hu, Markus W. Ribbe
    • Journal Title

      Nature Chem.

      Volume: 10 Issue: 5 Pages: 568-572

    • DOI

      10.1038/s41557-018-0029-4

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 有機金属化学と生物無機化学の境界を志向したものづくり:ニトロゲナーゼを題材に2020

    • Author(s)
      大木靖弘
    • Organizer
      徳島大学研究クラスター「有機合成化学を起点とするセンシング技術の開発と応用」特別講演会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Molybdenum-Containing Metal-Sulfur Clusters for Bio-Inspired N2 Activation2019

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      12th China-Japan Joint Symposium on Metal Cluster Compounds
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Organometallic Approach Toward Functional Analogues of the Nitrogenase Metallo-cofactors2019

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      第69回錯体化学討論会 シンポジウム” Metal-ligand cooperation:New design in the development of functional organometallic complexes”
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Bio-inspired N2 Activation by Cubic Metal-Sulfur Clusters2019

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      International Congress on Pure & Applied Chemistry (ICPAC) Yangon 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Iron-Based Hydride Clusters: Synthesis, Characterization, and Application in the Catalytic N2 Silylation2018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      International Workshop on New Developments and Prospects for the Future of Mossbauer Spectroscopy
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Iron-Based Hydride Clusters and Their Application in the Catalytic Silylation of N22018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      2018 Nankai International Symposium on Advanced Materials
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] C5Me5 (Cp*)-Supported Metal-Sulfur Clusters for N2 Activation2018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Molecular Metal-Chalcogenides for Bio-inspired Nitrogen Activation2018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 15th International Symposium on Inorganic Ring Systems (IRIS-15)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Cubic [Mo3S4M] Clusters with First-Row Transition Metals for Bio-inspired N2 Activation2018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 3rd Japan-UK Joint Symposium on Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2018-04-23   Modified: 2021-01-27  

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