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Synthesis and Properties of Metal-Sulfur Clusters Consisting of Multiple Components

Research Project

Project/Area Number 23685015
Research Category

Grant-in-Aid for Young Scientists (A)

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

Principal Investigator

OHKI Yasuhiro  名古屋大学, 理学(系)研究科(研究院), 准教授 (10324394)

Project Period (FY) 2011-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥28,990,000 (Direct Cost: ¥22,300,000、Indirect Cost: ¥6,690,000)
Fiscal Year 2013: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
Fiscal Year 2012: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
Fiscal Year 2011: ¥10,270,000 (Direct Cost: ¥7,900,000、Indirect Cost: ¥2,370,000)
Keywords鉄 / 硫黄 / クラスター / ニトロゲナーゼ / 一酸化炭素デヒドロゲナーゼ / 金属-硫黄クラスター / COデヒドロゲナーゼ
Research Abstract

Biological transformations of N2 and CO are mediated by the metallo-enzymes called nitrogenase and CO-dehydrogenase, respectively. Their active sites consist of sulfur, iron, and another transition metal, and their complex structures have been challenging synthetic targets. In this research project, we developed new synthetic reactions for Fe/S/O and V/Fe/S clusters in non-polar organic solvents. One of the important outcomes of this project is the synthesis of the [Fe8S6O] cluster which mimics the active site of nitrogenase. The bonding mode of its central oxygen atom gave us a clue to understand how the enzymatic active site works. Also to be noted is the synthesis of [VFe3S4-Fe] cluster which is structurally relevant to the active site of CO-dehydrogenase.

Report

(4 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • Research Products

    (37 results)

All 2014 2013 2012 2011 Other

All Journal Article (16 results) (of which Peer Reviewed: 16 results) Presentation (19 results) (of which Invited: 12 results) Remarks (2 results)

  • [Journal Article] Synthetic Analogues of the Active Sites of Nitrogenase and [NiFe] Hydrogenase2014

    • Author(s)
      Y. Ohki
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 87 Issue: 1 Pages: 1-19

    • DOI

      10.1246/bcsj.20130207

    • NAID

      130004153267

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Coupling of an N-Heterocyclic Carbene on Iron with Alkynes Forming η5-Cyclopentadienyl-Diìmine Ligands.2014

    • Author(s)
      T. Hatanaka, Y. Ohki, K. Tatsumi
    • Journal Title

      Angew. Chem. Int. Ed

      Volume: 53 Issue: 10 Pages: 2727-2729

    • DOI

      10.1002/ange.201309021

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dinuclear Iron (0) Complexes of N-Heterocyclic Carbenes2014

    • Author(s)
      T. Hashimoto, R. Hoshino, T. Hatanaka, Y. Ohki, K. Tatsumi
    • Journal Title

      Organometallics

      Volume: 33 Issue: 4 Pages: 921-929

    • DOI

      10.1021/om401039z

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] New Synthetic Routes to Metal-Sulfur Clusters Relevant to the Nitrogenase Metallo-Clusters.2013

    • Author(s)
      Y. Ohki, K. Tatsumi
    • Journal Title

      Anorg. Allg. Chem

      Volume: 639 Issue: 8-9 Pages: 1340-1349

    • DOI

      10.1002/zaac.201300081

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Snthesis of Coordinatively Unsaturated Half-Sandwich Iron Silyl Complexes Having an N-Heterocyclic Carbene Ligand and Their Reactions with H2.2013

    • Author(s)
      T. Hatanaka, Y. Ohki, K. Tatsumi
    • Journal Title

      Eur. J. Inorg. Chem

      Volume: 33 Issue: 22-23 Pages: 3966-3971

    • DOI

      10.1002/ejic.201300045

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catlytic Generation of Borenium Ions by Cooperative B-H Bond Activation : The Elusive Direct Electrophilic Borylation of Nitrogen Heterocycles with Pinacolborane.2013

    • Author(s)
      T. Stahl, K. e Müther, Y. Ohki, K. Tatsumi, M. Oestreich
    • Journal Title

      J. Am. Chem. Soc

      Volume: 135 Issue: 30 Pages: 10978-10981

    • DOI

      10.1021/ja405925w

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Nitrogenase Cluster Model [Fe8S6O] with an Oxygen Unsymmetrically Bridging two Proto-Fe4S3 Cubes: Relevancy to the Substrate-Binding Mode of the FeMo-cofactor2012

    • Author(s)
      S. Ohta, Y. Ohki, R. E. Cramer, and K. Tatsumi
    • Journal Title

      Inorg. Chem

      Volume: 51 Issue: 21 Pages: 11217-11219

    • DOI

      10.1021/ic301348f

    • Related Report
      2013 Final Research Report 2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Formation of a Nitrogenase P-cluster [Fe_8S_7] Core via Reductive Fusion of Two All-Fenic [Fe_4S_4] Clusters2012

    • Author(s)
      Y. Ohki, K. Tanifuji, N. Yamada, K. Tatsumi
    • Journal Title

      Chemistry an Asian Journal

      Volume: 7 Issue: 10 Pages: 2222-2224

    • DOI

      10.1002/asia.201200568

    • Related Report
      2013 Final Research Report 2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxido-bridged Di-, Tri-, and Tetra-nuclear Iron Complexes Bearing Bis (trimethylsilyl)amide and Thiolate Ligands2012

    • Author(s)
      Shun Ohta, Saori Yokozawa, Yasuhiro Ohki, Kazuyuki Tatsumi
    • Journal Title

      Inorg.Chem.

      Volume: 51 Issue: 4 Pages: 2645-2651

    • DOI

      10.1021/ic2025928

    • Related Report
      2013 Final Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Naphthalene and Anthracene Complexes Sandwiched by Two Cp*FeI Fragments: Strong Electronic Coupling Between the FeI Centers2012

    • Author(s)
      T. Hatanaka et al
    • Journal Title

      Chem. Asian J.

      Volume: 7 Issue: 6 Pages: 1231-1242

    • DOI

      10.1002/asia.201101037

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Non-Centrosymmetric Coordination Polymer with a Highly Hindered Octahedral Copper Center Bridged by Mandelate2012

    • Author(s)
      M. Moriya, S. Tominaga, T.i Hashimoto, K. Tanifuji, T. Matsumoto, Y. Ohki, K. Tatsumi, J. Kaneshiro, Y. Uesu, W. Sakamoto, T. Yog
    • Journal Title

      Inorg. Chem

      Volume: 51 Issue: 8 Pages: 4689-4693

    • DOI

      10.1021/ic202669r

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Base-Free Dehydrogenative Coupling of Enolizable Carbonyl Compounds with Silanes Involving Catalytic Generation of the Silicon Electrophile2012

    • Author(s)
      C. David F. Konigs, Hendrik F. T. Klare, Yasuhiro Ohki, Kazuyuki Tatsumi, Martin Oestreich
    • Journal Title

      Org. Lett

      Volume: 14 Issue: 11 Pages: 2842-2845

    • DOI

      10.1021/ol301089r

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Bis(N-heterocyclic carbene) Complexes of Iron(II) and Their Application in Hydrosilylation and Transfer Hydrogenation2012

    • Author(s)
      T. Hashimoto, S. Urban, R. Hoshino, Y. Ohki, K. Tatsumi, F. Glorius
    • Journal Title

      Organometallics

      Volume: 31 Issue: 12 Pages: 4474-4479

    • DOI

      10.1021/om300298q

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An Iron(II) Complex of Diamine-Bridged Bis-N-Heterocyclic Carbene2012

    • Author(s)
      C. Grohmann, T. Hashimoto, R. Frohlich, Y. Ohki, K. Tatsumi, F. Glorius
    • Journal Title

      Organometallics

      Volume: 31 Issue: 23 Pages: 8047-8050

    • DOI

      10.1021/om300888q

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthetic Analogues of [Fe_4S_4(Cys)_3(His)] in Hydrogenases and [Fe_4S_4(Cys)_4]in HiPIP Derived from All-Ferric [Fe_4S_4{N(SiMe_3)_2}_4]2011

    • Author(s)
      Yasuhiro Ohki, Kazuki Tanifuji, Norihiro Yamada, Motosuke Imada, Tomoyuki Tajima, Kazuyuki Tatsumi
    • Journal Title

      Proc.Natl.Acad.Sci.U.S.A.

      Volume: 108 Issue: 31 Pages: 12635-12640

    • DOI

      10.1073/pnas.1106472108

    • Related Report
      2013 Final Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cooperative Catalytic Activation of Si-H Bonds by a Polar Ru-S Bond : Regioselective Low-Temperature C-H Silylation of Indoles under Neutral Conditions by a Friedel-Crafts Mechanism2011

    • Author(s)
      Hendrik F.T.Klare, Martin Oestreich, Jun-ichi Ito, Hisao Nishiyama, Yasuhiro Ohki, Kazuyuki Tatsumi
    • Journal Title

      J.Am.Chem.Soc.

      Volume: 133 Issue: 10 Pages: 3312-3315

    • DOI

      10.1021/ja111483r

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] 酵素活性中心を模倣する鉄-硫黄クラスターの合成と骨格変換2014

    • Author(s)
      大木靖弘
    • Organizer
      東京工業大学資源化学研究所講演会
    • Place of Presentation
      東京工業大学資源化学研究所
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 配位不飽和錯体のルテニウム-硫黄部位を反応場とするE-H(E = H, Si, B)結合活性化反応2014

    • Author(s)
      大木靖弘
    • Organizer
      新学術領域研究「分子活性化」第6回公開シンポジウム
    • Place of Presentation
      東京工業大学
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Synthesis of Iron-Sulfur Clusters Mimicking the Nitrogenase Metallo-Clusters2013

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      第63回錯体化学討論会–日韓セッション
    • Place of Presentation
      琉球大学
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis and Characterization of Iron-Sulfur Cluster Molecules Mimicking the Nitrogenase Metallo-Clusters2013

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Collaborative Conference on 3D and Materials Research 2013
    • Place of Presentation
      Jeju, Korea
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis and Characterization of Iron-Sulfur Cluster Molecules Mimicking the Nitrogenase Metallo-Clusters2013

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Collaborative Conference on 3D and Materials Research 2013
    • Place of Presentation
      Jeju
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 酵素活性中心をなす鉄-硫黄クラスターの自在構築と自在変形への挑戦2013

    • Author(s)
      大木靖弘
    • Organizer
      東京工業大学大学院理工学研究科化学専攻講演会
    • Place of Presentation
      東京工業大学
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] [NiFe]ヒドロゲナーゼの活性部位モデルとなる有機遷移金属錯体2013

    • Author(s)
      大木靖弘
    • Organizer
      第112回触媒討論会
    • Place of Presentation
      秋田大学
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Synthesis of Iron-Sulfur Clusters Mimicking the Nitrogenase Metallo-Clusters2013

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      第63回錯体化学討論会
    • Place of Presentation
      琉球大学
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] N-Heterocyclic Carbene Complexes of Iron for Small Molecule Activation and Transformation2013

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      新学術領域研究「分子活性化」第4回若手シンポジウム
    • Place of Presentation
      鹿児島
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 酵素活性中心の構造を再現する鉄-硫黄クラスターの精密無機合成2013

    • Author(s)
      大木靖弘
    • Organizer
      九州大学先導物質化学研究所特別講演会
    • Place of Presentation
      九州大学先導物質化学研究所
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] [NiFe]ヒドロゲナーゼ活性部位のモデル構築と機能の模倣2012

    • Author(s)
      大木靖弘
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学
    • Year and Date
      2012-03-25
    • Related Report
      2011 Annual Research Report
  • [Presentation] 酵素活性中心を模倣する鉄-硫黄クラスターの無機合成2012

    • Author(s)
      大木靖弘
    • Organizer
      京都大学元素化学国際研究センター講演会
    • Place of Presentation
      京都大学化学研究所
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] ニトロゲナーゼ活性部位の人工構築を志向した鉄-硫黄クラスター合成反応2012

    • Author(s)
      大木靖弘
    • Organizer
      第3回統合物質シンポジウム
    • Place of Presentation
      西新プラザ(福岡)
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Half-Sandwich Iron Complexes for C-H Bond Activation and Borylation of Heteroarenes2012

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      17th Malaysian Chemical Congress 2012
    • Place of Presentation
      Kuala Lumpur, Malaysia
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Half-Sandwich Iron Complexes for C-H Bond Activation and Borylation of Heteroarenes2012

    • Author(s)
      Yasuhiro Ohki
    • Organizer
      Cambodian Malaysian Chemical Conference 2012
    • Place of Presentation
      Siem Reap, Cambodia
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Chemistry of the Unique Cluster Active Sites in Reductases2011

    • Author(s)
      Kazuyuki Tatsumi, Yasuhiro Ohki
    • Organizer
      The 3^<rd> Asian Conference on Coordination Chemistry
    • Place of Presentation
      Delhi
    • Year and Date
      2011-10-19
    • Related Report
      2011 Annual Research Report
  • [Presentation] N-ヘテロ環カルベン配位子を持つ低原子価鉄錯体の合成と性質2011

    • Author(s)
      大木靖弘、星野涼子、橋本享昌、畑中翼、巽和行
    • Organizer
      第108回触媒討論会
    • Place of Presentation
      北見工業大学
    • Year and Date
      2011-09-21
    • Related Report
      2011 Annual Research Report
  • [Presentation] Reactions at the Ru-S Bonds of Coordinatively Unsaturated Ruthenium Complexes Having a Tethered 2,6-Dimesitylphenyl Thiolate2011

    • Author(s)
      Yasuhiro Ohki, Hendrik F.T.Klare, Martin Oestreich, Yuko Takikawa, Jun-ichi Ito, Hisao Nishiyama, Kazuyuki Tatsumi
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学
    • Year and Date
      2011-09-08
    • Related Report
      2011 Annual Research Report
  • [Presentation] Chemistry of the Unique Cluster Active Sites in Reductases2011

    • Author(s)
      Kazuyuki Tatsumi and Yasuhiro Ohki
    • Organizer
      3rd Asian Conference on Coordination Chemistry (ACCC3)
    • Place of Presentation
      New Delhi, India
    • Related Report
      2013 Final Research Report
  • [Remarks] ホームページ等

    • URL

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

    • Related Report
      2013 Final Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2011 Annual Research Report

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Published: 2011-04-06   Modified: 2019-07-29  

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