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Synthesis of Cp*-supported metal-sulfur clusters as functional analogues of the active site of nitrogenase

Research Project

Project/Area Number 16H04116
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionNagoya University

Principal Investigator

Ohki Yasuhiro  名古屋大学, 理学研究科, 准教授 (10324394)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,030,000 (Direct Cost: ¥13,100,000、Indirect Cost: ¥3,930,000)
Fiscal Year 2018: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2017: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2016: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Keywords窒素固定化 / ニトロゲナーゼ / 金属-硫黄クラスター / モリブデン / チタン / 窒素 / 硫黄 / クラスター / 鉄 / 窒素活性化 / 金属 / 酵素モデル
Outline of Final Research Achievements

Inorganic components consisting of multiple transition metals and sulfur atoms are designated as metal-sulfur clusters, which are essential for various biological functions. The largest biological metal-sulfur cluster thus far structurally identified is the nitrogenase FeMo-cofactor, which catalyzes the reduction of N2 into NH3 under physiological conditions. Although various metal-sulfur clusters structurally relevant to FeMo-cofactor have been synthesized over the years, their use in the activation of N2 has proven challenging to realize, and even the FeMo-cofactor extracted from the protein to organic solvents has not been found to reduce N2. In this research project, we synthesized a series of Cp* (C5Me5)-supported cubic [Mo3S4M] clusters, and demonstrated the activation of N2 and its conversion into NH3 and N2H4 on the [Mo3S4Ti] variant. This result represents an initial step toward modeling the reducing function of the FeMo-cofactor.

Academic Significance and Societal Importance of the Research Achievements

本研究では、多数の金属原子と硫黄原子を集めた「金属-硫黄クラスター」分子を用いて、N2を捕捉し還元できることを世界で初めて実証した。この研究をさらに発展させることで、酵素タンパク中で金属-硫黄クラスターがどのようにN2を捕捉し還元するかを明らかにすることや、酵素のN2還元機能を人工的に再現することが可能になると期待される。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (34 results)

All 2019 2018 2017 2016 Other

All Int'l Joint Research (3 results) Journal Article (13 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 13 results,  Open Access: 1 results,  Acknowledgement Compliant: 6 results) Presentation (17 results) (of which Int'l Joint Research: 12 results,  Invited: 17 results) Remarks (1 results)

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

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] University of California, Irvine(米国)

    • Related Report
      2017 Annual Research Report
  • [Int'l Joint Research] UC Irvine(米国)

    • Related Report
      2016 Annual Research Report
  • [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
  • [Journal Article] [Fe4] and [Fe6] Hydride Clusters Supported by Phosphines: Synthesis, Characterization, and Application in N2 Reduction2017

    • Author(s)
      Ryoichi Araake, Kazuki Sakadani, Mizuki Tada, Yoichi Sakai, Yasuhiro Ohki
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 139 Issue: 15 Pages: 5596-5606

    • DOI

      10.1021/jacs.7b01965

    • NAID

      120006318713

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and characterization of bio-inspired [Mo2Fe2] hydride clusters and their application to the catalytic silylation of N22017

    • Author(s)
      Yasuhiro Ohki, Yuna Araki, Mizuki Tada, Yoichi Sakai
    • Journal Title

      Chem. Eur. J.

      Volume: 23 Issue: 53 Pages: 13240-13248

    • DOI

      10.1002/chem.201702925

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] High-Efficiency Reduction of C1 Substrates to Hydrocarbons by the Homometallic Precursor and Synthetic Mimic of the Nitrogenase Cofactor2017

    • Author(s)
      Nathaniel S. Sickerman, Kazuki Tanifuji, Yasuhiro Ohki, Kazuyuki Tatsumi, Markus W. Ribbe, Yilin Hu
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 139 Issue: 2 Pages: 603-606

    • DOI

      10.1021/jacs.6b11633

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] N-Heterocyclic Carbene Complexes of Three- and Four-Coordinate Fe(I)2016

    • Author(s)
      Yasuhiro Ohki, Ryoko Hoshino, Kazuyuki Tatsumi
    • Journal Title

      Organometallics

      Volume: 35 Issue: 10 Pages: 1368-1375

    • DOI

      10.1021/acs.organomet.5b01025

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Interconversion Between [Fe4S4] and [Fe2S2] Clusters Bearing Amide Ligands2016

    • Author(s)
      Kazuki Tanifuji, Shunichi Tajima, Yasuhiro Ohki, Kazuyuki Tatsumi
    • Journal Title

      Inorg. Chem.

      Volume: 55 Issue: 9 Pages: 4512-4518

    • DOI

      10.1021/acs.inorgchem.6b00352

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Dimethylmanganese(II) Complexes bearing N-Heterocyclic Carbenes and Nucleophilic Substitution Reaction of Tetraalkoxysilanes by Diorganomanganese(II) Complexes2016

    • Author(s)
      Takayoshi Hashimoto, Yuko Kawato, Yumiko Nakajima, Yasuhiro Ohki, Kazuyuki Tatsumi, Wataru Ando, Kazuhiko Sato, Shigeru Shimada
    • Journal Title

      J. Organomet. Chem.

      Volume: 820 Pages: 14-19

    • DOI

      10.1016/j.jorganchem.2016.07.025

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Structure and reactivity of an asymmetric synthetic mimic of nitrogenase cofactor2016

    • Author(s)
      Kazuki Tanifuji, Nathaniel Sickerman, Chi Chung Lee, Takayuki Nagasawa, Kosuke Miyazaki, Yasuhiro Ohki, Kazuyuki Tatsumi, Yilin Hu, Markus W. Ribbe
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 55 Issue: 50 Pages: 15633-15636

    • DOI

      10.1002/anie.201608806

    • NAID

      120005981222

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Co6H8(PiPr3)6: A Cobalt Octahedron Having Face-Capping Hydrides2016

    • Author(s)
      Yasuhiro Ohki, Yuki Shimizu, Ryoichi Araake, Mizuki Tada, W. M. C. Sameera, Jun-Ichi Ito, Hisao Nishiyama
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 55 Issue: 51 Pages: 15821-15825

    • DOI

      10.1002/anie.201608262

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [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
  • [Presentation] [Fe4] and [Fe6] Hydride Clusters as Catalyst Precursors for N2 Silylation2018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 2nd Base Metal Catalysis Symposium ~After Discussion~
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bio-inspired [Mo2Fe2] Hydride Clusters: Synthesis and Application in the Catalytic Silylation of N22018

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      International Congress on Pure & Applied Chemistry (ICPAC) 2018
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Fe4 and Fe6 Hydride Clusters Supported by Phosphines: Synthesis, Characterization, and Application in the Conversion of N22017

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      International Symposium on Pure & Applied Chemistry (ISPAC) 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bio-inspired Transition Metal Cluster Molecules: Synthesis and Application in N2 Transformation2017

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Telluride Science Research Center workshop on “Control of Proton and Electron Transfers in Redox Catalysis”
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Hydride-Supported [Fe4] and [Fe6] Clusters and Their Application in the Catalytic N2 Silylation2017

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 11th Japan-China Symposium on Cluster Science
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 鉄系ヒドリドクラスター分子の創製と触媒的N2還元反応2017

    • Author(s)
      大木靖弘
    • Organizer
      京都大学化学研究所セミナー
    • Place of Presentation
      京都大学化学研究所
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Synthesis, Structures, and Reactivities of Iron and Cobalt Hydride Clusters Supported by Phosphines2016

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Pre-ICMM 2016 in Nagoya
    • Place of Presentation
      Nagoya University
    • Year and Date
      2016-09-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Toward Functional Mimics of Nitrogenase: Synthesis, Structures, and Reactivities of New Molecular Metal-Sulfur Clusters2016

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      International Symposium on Pure & Applied Chemistry 2016
    • Place of Presentation
      Kuching (Malaysia)
    • Year and Date
      2016-08-15
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ニトロゲナーゼの機能モデルを志向した金属-硫黄クラスター2016

    • Author(s)
      大木靖弘
    • Organizer
      日本化学会青森地区講演会
    • Place of Presentation
      弘前大学
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] ニトロゲナーゼの酵素機能に学ぶ金属クラスター化合物の合成2016

    • Author(s)
      大木靖弘
    • Organizer
      近畿大学応用化学セミナー
    • Place of Presentation
      近畿大学
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 化学の視点からニトロゲナーゼ活性中心の機能を考察し模倣する2016

    • Author(s)
      大木靖弘
    • Organizer
      第3回エネルギー物質創成のための触媒科学技術研究会
    • Place of Presentation
      名古屋工業大学
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 窒素固定化酵素ニトロゲナーゼの機能に学ぶ分子性クラスターの創製2016

    • Author(s)
      大木靖弘
    • Organizer
      錯体化学若手の会北陸支部勉強会
    • Place of Presentation
      金沢大学
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Remarks]

    • URL

      http://inorg.chem.nagoya-u.ac.jp/members/ohki/ohki-j-frame.html

    • Related Report
      2017 Annual Research Report

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Published: 2016-04-21   Modified: 2022-05-20  

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