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2012 Fiscal Year Final Research Report

Development of Metal -Sulfur Cluster Molecules Leading to Novel Nitrogen Fixation

Research Project

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Project/Area Number 21350033
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

SEINO Hidetake  東京大学, 生産技術研究所, 助教 (50292751)

Co-Investigator(Renkei-kenkyūsha) MIZOBE Yasushi  東京大学, 生産技術研究所, 教授 (40175609)
Project Period (FY) 2009 – 2012
Keywords有機金属化学 / 合成化学 / 触媒・化学プロセス / 金属-硫黄クラスター / 窒素固定酵素 / 水素生成 / 小分子活性化
Research Abstract

Aiming at the reaction sites for conversion of nitrogen, transition metal-sulfur clusters were investigated as the models for the active site of nitrogenase, which was assembled from multiple metal and sulfur atoms. Stepwise synthetic routes were applied to construct the cluster skeletons, in which four metal and four sulfur atoms were located alternately at the corners of a cube. Reactivity of the cluster that could activate coordinated nitrogen molecule was revealed. Analogous clusters composed of different metal elements were prepared, and specific binding and conversion of hydrazine and carbon monoxide etc. on these clusters were achieved.

  • Research Products

    (14 results)

All 2013 2012 2011 2010 2009

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (7 results) Book (1 results)

  • [Journal Article] Preparation of Incomplete Cubane-Type Ru_2M(μ_3-S)(μ_2-C1)_3 Clusters (M = Sb, Bi) and Isolation of the Ru_2Sb Cluster Having a Novel μ_3-SO Ligand2011

    • Author(s)
      Kazumasa Oya, Hidetake Seino, Midori Akiizumi, Yasushi Mizobe
    • Journal Title

      Functions in Oxygen Atom Transfer and Catalytic Oxidation of PPh_3 to O=PPh_3 by Molecular O_2; Organometallics

      Volume: 30(11) Pages: 2939-2946

    • DOI

      DOI:10.1021/om101095a

    • Peer Reviewed
  • [Journal Article] Catalytic functions of cubane-type M_4S_4 clusters2011

    • Author(s)
      Hidetake Seino, Masanobu Hidai
    • Journal Title

      Chemical Science

      Volume: 2(5) Pages: 847-857

    • DOI

      DOI:10.1039/c0sc00545b

    • Peer Reviewed
  • [Journal Article] Core Conversion Reactions of the Cubane-Type Metal-Sulfido Clusters: Shape Shift, Contraction, and Expansion of the MM'Re Cubanes (M = Ir, Rh, Ru; M' = Pt, Pd)2010

    • Author(s)
      Rie Shibata, Hidetake Seino, Shunpei Fujii, Yasushi Mizobe
    • Journal Title

      Inorganic Chemistry

      Volume: 49(15) Pages: 6889-6896

    • DOI

      DOI:10.1021/ic100339f

    • Peer Reviewed
  • [Journal Article] Incorporation of Fe into the void corner of the incomplete cubane-type Ir_3(SH)_3 sulfido-hydrosulfido cluster to give new cubane-type Ir_3FeS_4 clusters2010

    • Author(s)
      Hidetake Seino, Hiroyuki Mori, Aya Shinozaki, Yasushi Mizobe
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 695(15-16) Pages: 1878-1882

    • DOI

      DOI:10.1016/j.jorganchem.2010.04.030

    • Peer Reviewed
  • [Journal Article] Theoretical Study on Activation and Protonation of Dinitrogen on Cubane-Type MIr_3S_4 Clusters (M = V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, and W)2010

    • Author(s)
      Hiromasa Tanaka, Fumihiro Ohsako, Hidetake Seino, Yasushi Mizobe, Kazunari Yoshizawa
    • Journal Title

      Inorganic Chemistry

      Volume: 49(5) Pages: 2464-2470

    • DOI

      DOI:10.1021 /ic902414n

    • Peer Reviewed
  • [Journal Article] Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine co-ligand and its transformation into MoRh_2 and MoIr_2 mixed-metal sulfido clusters2009

    • Author(s)
      Kentaro Iwasa, Hidetake Seino, Fumiya Niikura, Yasushi Mizobe
    • Journal Title

      Dalton Transactions

      Volume: 31 Pages: 6134-6140

    • DOI

      DOI:10.1039/b902386k

    • Peer Reviewed
  • [Presentation] 貴金属元素を含むキュバン型スルフィドクラスターと含窒素小分子の反応2012

    • Author(s)
      清野秀岳
    • Organizer
      第43回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2012-11-11
  • [Presentation] Reactions of Cubane-type MoIr_3S_4 and TaIr_3S4 Clusters with Hydrazine Compounds2012

    • Author(s)
      Hidetake Seino, Yusuke Watanabe, Yuta Manaka, Yasushi Mizobe
    • Organizer
      40th International Conference on Coordination Chemistry
    • Place of Presentation
      バレンシア(スペイン)
    • Year and Date
      2012-09-12
  • [Presentation] キュバン型TaIr_3S_4クラスターの合成と架橋ヒドラジン配位子を有するダブルキュバン構造の形成2011

    • Author(s)
      柴田祐介、清野秀岳、溝部裕司
    • Organizer
      第61回錯体化学討論会
    • Place of Presentation
      岡山理科大学
    • Year and Date
      2011-09-19
  • [Presentation] カテコラート配位子を有するキュバン型MoIr_3S_4スルフィドクラスターによるヒドラジンの触媒的還元反応2011

    • Author(s)
      清野秀岳、間中勇太、溝部裕司
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      神奈川大学・横浜キャンパス
    • Year and Date
      2011-03-29
  • [Presentation] 窒素分子配位キュバン型金属‐硫黄クラスターの反応性とプロトン還元における触媒機能2010

    • Author(s)
      清野秀岳、平田恵一、森浩之、溝部裕司
    • Organizer
      第57回有機金属化学討論会
    • Place of Presentation
      中央大学多摩キャンパス
    • Year and Date
      20109018
  • [Presentation] Preparation of Metal-Sulfido Clusters as the New Models of the Active Site of Nitrogenase2010

    • Author(s)
      Yasushi Mizobe, Hidetake Seino
    • Organizer
      Pacifichem 2010
    • Place of Presentation
      ホノルル(アメリカ合衆国)
    • Year and Date
      2010-12-17
  • [Presentation] Syntheses of the Cubane-type Transition-Metal Sulfido Clusters for Activation of Molecular Dinitrogen2009

    • Author(s)
      Hidetake Seino, Yasushi Mizobe
    • Organizer
      The 14th International Conference on Biological Inorganic Chemistry
    • Place of Presentation
      名古屋国際会議場
    • Year and Date
      2009-07-26
  • [Book] Metal-Sulfur Clusters as the Model for the Active Sites of Metalloenzymes, in "Handbook of Chalcogen Chemistry," F. Devillanova, W.-W. Du Mont Eds.2013

    • Author(s)
      Yasushi Mizobe, Hidetake Seino
    • Total Pages
      18
    • Publisher
      RSC Publishing

URL: 

Published: 2014-08-29  

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