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Synthesis of Metal-Nanoclusters of Iron Group Metals

Research Project

Project/Area Number 20K21207
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
Research InstitutionKyoto University

Principal Investigator

Ohki Yasuhiro  京都大学, 化学研究所, 教授 (10324394)

Project Period (FY) 2020-07-30 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2022: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2021: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2020: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords鉄 / ホスフィン / ホウ素 / アミド / コバルト / ニッケル / クラスター / ヒドリド
Outline of Research at the Start

金属ナノクラスターの構造と反応性や物性の関係を明らかにして基礎を固めることを目指し、本研究では1nmを前後するクラスターを、構造や組成が規定される「分子」として、先例がない鉄族金属元素(Fe, Co等)を用いて合成する。標的クラスターの合成に向けては、非極性の有機溶媒中で無電荷の化合物だけを用いる、代表者独自の反応を発展させる。

Outline of Final Research Achievements

This research study provided the following three representative outcomes. The first one is the synthesis of an Fe-cluster complex using a primary phosphine with a bulky aromatic group. The second result is the discovery of the skeletal rearrangement of a planar Fe6 cluster complex into a triangular complex. The third achievement is the detailed analysis of the catalytically active Fe-cluster species in the silylation of N2.

Academic Significance and Societal Importance of the Research Achievements

窒素分子や二酸化炭素の還元反応は、エネルギー変換/貯蔵の観点やSDGsの観点で社会的な注目を集めている。窒素分子をアンモニアへ還元する酵素反応や工業反応、二酸化炭素を一酸化炭素へ還元する酵素反応、一酸化炭素から液体炭化水素を合成する工業反応の全てに関わる金属元素が鉄であり、これらの反応の高効率化に向けた触媒候補になり得るのが、金属塊より反応性が高く、複数の金属原子が反応に関わる可能性があるのが金属クラスター錯体である。また、構造と組成が一義的に決まる金属クラスター錯体は、反応性の詳細を確認し易く、高効率触媒を開発するための基礎的な知見も提供すると期待できる。

Report

(4 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (30 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (3 results) Journal Article (9 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 9 results,  Open Access: 1 results) Presentation (15 results) (of which Int'l Joint Research: 8 results,  Invited: 15 results) Book (1 results) Remarks (2 results)

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

    • Related Report
      2022 Annual Research Report
  • [Int'l Joint Research] University of Colombo(スリランカ)

    • Related Report
      2022 Annual Research Report
  • [Int'l Joint Research] University of Hawaii/University of California, Irvine(米国)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Activation of unsaturated small molecules by bio-relevant multinuclear metal-sulfur clusters2023

    • Author(s)
      Tanifuji Kazuki、Ohta Shun、Ohki Yasuhiro、Seino Hidetake
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 475 Pages: 214838-214838

    • DOI

      10.1016/j.ccr.2022.214838

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes2022

    • Author(s)
      Ohki Yasuhiro、Munakata Kenichiro、Matsuoka Yuto、Hara Ryota、Kachi Mami、Uchida Keisuke、Tada Mizuki、Cramer Roger E.、Sameera W. M. C.、Takayama Tsutomu、Sakai Yoichi、Kuriyama Shogo、Nishibayashi Yoshiaki、Tanifuji Kazuki
    • Journal Title

      Nature

      Volume: 607 Issue: 7917 Pages: 86-90

    • DOI

      10.1038/s41586-022-04848-1

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] CO Binding onto Heterometals of [Mo3S4M] (M = Fe, Co, Ni) Cubes2022

    • Author(s)
      K. Tanifuji, Y. Sakai, Y. Matsuoka, M. Tada, W. M. C. Sameera, Y. Ohki
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 95 Issue: 8 Pages: 1190-1195

    • DOI

      10.1246/bcsj.20220143

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Incorporation of an Asymmetric Mo-Fe-S Cluster as an Artificial Cofactor into Nitrogenase2022

    • Author(s)
      Tanifuji Kazuki、Jasniewski Andrew J.、Lee Chi Chung、Solomon Joseph B.、Nagasawa Takayuki、Ohki Yasuhiro、Tatsumi Kazuyuki、Hedman Britt、Hodgson Keith O.、Hu Yilin、Ribbe Markus W.
    • Journal Title

      ChemBioChem

      Volume: 23 Issue: 19

    • DOI

      10.1002/cbic.202200384

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Diastereo- and Enantioselective Metathesis Dimerization/Kinetic Resolution of Racemic Planar-Chiral Vinylferrocenes2022

    • Author(s)
      Nishimoto Koji、Taue Haruka、Ohji Takehito、Funakoshi Sayaka、Ohki Yasuhiro、Ogasawara Masamichi
    • Journal Title

      Organic Letters

      Volume: 24 Issue: 40 Pages: 7355-7360

    • DOI

      10.1021/acs.orglett.2c02888

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Flow‐Chemistry‐Enabled Synthesis of 5‐Diethylboryl‐2,3′‐bipyridine and Its Self‐Assembly Dynamics2022

    • Author(s)
      Wakabayashi Shigeharu、Takumi Masahiro、Kamio Shintaro、Wakioka Masayuki、Ohki Yasuhiro、Nagaki Aiichiro
    • Journal Title

      Chemistry A European Journal

      Volume: 29 Issue: 9

    • DOI

      10.1002/chem.202202882

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Monophosphaferrocenes Revisited2022

    • Author(s)
      Masaoka Kakeru、Ohkubo Manami、Taue Haruka、Wakioka Masayuki、Ohki Yasuhiro、Ogasawara Masamichi
    • Journal Title

      ChemistrySelect

      Volume: 7 Issue: 3

    • DOI

      10.1002/slct.202104472

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Tracing the incorporation of the “ninth sulfur” into the nitrogenase cofactor precursor with selenite and tellurite2021

    • Author(s)
      Tanifuji Kazuki、Jasniewski Andrew J.、Villarreal David、Stiebritz Martin T.、Lee Chi Chung、Wilcoxen Jarett、Okhi Yasuhiro、Chatterjee Ruchira、Bogacz Isabel、Yano Junko、Kern Jan、Hedman Britt、Hodgson Keith O.、Britt R. David、Hu Yilin、Ribbe Markus W.
    • Journal Title

      Nature Chemistry

      Volume: 13 Issue: 12 Pages: 1228-1234

    • DOI

      10.1038/s41557-021-00799-8

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A dinuclear Mo2H8 complex supported by bulky C5H2 tBu3 ligands2020

    • Author(s)
      Yasuhiro Ohki, Kodai Ishihara, Moeko Yaoi, Mizuki Tada, W. M. C. Sameera, Roger E. Cramer
    • Journal Title

      Chem. Commun.

      Volume: 56 Issue: 58 Pages: 8035-8038

    • DOI

      10.1039/d0cc03274c

    • NAID

      120006941036

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 酵素模倣型クラスター錯体の合成と不活性小分子の還元2023

    • Author(s)
      大木 靖弘
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 自然に学び超える高難度還元反応の触媒開発へ2022

    • Author(s)
      大木 靖弘
    • Organizer
      Roadmap to 2050 カーボン・ニュートラル推進連続セミナー 第6回「触媒を用いたグリーンイノベーションへの挑戦」
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 三元系金属-ヘテロ原子化合物による窒素分子の活性化と変換2022

    • Author(s)
      大木 靖弘
    • Organizer
      近畿化学協会ヘテロ原子部会第一回懇話会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Nitrogen Activation and Conversion by the Fe Sites of Biomimetic Mo-Fe-S Cubes2022

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 8th Asian Conference on Coordination Chemistry (ACCC8)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] The very first step toward mimicking the biological nitrogen fixation2022

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Sri Lanka Association for the Advancement of Science (SLAAS) webinar “Frontiers in Chemistry”
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 立方体型Mo-Fe-Sクラスター錯体による触媒的なN2シリル化反応2022

    • Author(s)
      大木 靖弘
    • Organizer
      名古屋大学学際統合物質科学研究機構キックオフシンポジウム
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Bio-inspired Cubic Metal-Sulfur Clusters for N2 Activation2022

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      UNIST-Kyoto Symposium 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Activation and Reduction of N2 by Bioinspired Metal-Sulfur Clusters2022

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      The 19th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Biomimetic [Mo3S4Fe] Cubes for Catalytic N2 Silylation2022

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      10th Asian Biological Inorganic Chemistry Conference (AsBIC10)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bio-inspired Cubic Metal-Sulfur Clusters for N2 Activation2022

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      ACS Meeting Spring 2022
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Hydride- or sulfur-supported Fe-containing cluster molecules for nitrogen reduction2021

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 金属-硫黄クラスターによる小分子変換反応2021

    • Author(s)
      大木 靖弘
    • Organizer
      近畿化学協会有機金属部会2021年度第4回例会
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] 金属-硫黄クラスター錯体による小分子活性化2021

    • Author(s)
      大木 靖弘
    • Organizer
      有機合成化学研究所講演会(第36回)
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] 有機金属化学・錯体化学・生化学をつなぐ金属-硫黄クラスター錯体2021

    • Author(s)
      大木 靖弘
    • Organizer
      有機合成化学協会第33回若手研究者のためのセミナー
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] Activation of N2 and Small Molecules by Metal-Sulfur Cluster Molecules2021

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      LHFA virtual seminar
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Book] Adv. Organomet. Chem.2022

    • Author(s)
      W. M. C. Sameera, Youhei Takeda, Yasuhiro Ohki
    • Publisher
      Springer-Nature
    • Related Report
      2022 Annual Research Report
  • [Remarks] 京都大学化学研究所大木研究室

    • URL

      http://om.kuicr.kyoto-u.ac.jp

    • Related Report
      2021 Research-status Report
  • [Remarks]

    • URL

      http://om.kuicr.kyoto-u.ac.jp

    • Related Report
      2020 Research-status Report

URL: 

Published: 2020-08-03   Modified: 2024-01-30  

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