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Design of Coordinatively Unsaturated Iron Species for Homogeneous Catalysis

Research Project

Project/Area Number 22655029
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyushu University

Principal Investigator

NAGASHIMA Hideo  九州大学, 先導物質化学研究所, 教授 (50159076)

Project Period (FY) 2010 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥3,460,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥360,000)
Fiscal Year 2011: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2010: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywords元素戦略 / 鉄 / 分子触媒 / 酸化還元 / 共役付加 / エノレート / 鉄錯体 / 鉄触媒 / カップリング / 1,2-付加 / エノレート生成
Research Abstract

Three types of coordinatively unsaturated iron species were designed by appropriate choice of auxialiry ligands, and their reactivity towards alkenes and related unsaturated compounds was investigated. Triazacyclononane(TACN) derivatives were a good ligand for Fe(II) complexes. Coordinatively unsaturated 16e-(TACN) FeX2 species behaved as a catalyst for atom transfer radical polymerization. Two concepts for generation of 16e-Fe(II) species were proposed ; one was based on favorable equiliblim between a halogen-bridged dimer and a catalytically active monomer controlled by steric bulkiness of nitrogen substituents of TACN, whereas another was stabilization of active monomeric species by weakly coordinating ligands. Treatment of a 14e-organoiron complex bearing two mesityl groups and a tetraethylenediamine ligand with electron deficient alkenes resulted in coupling reaction of the mesityl ligands as well as conjugate addition of a mesityl group toα,β-unsaturated ketones. Disilametallacylic 16e-Fe(II) species was generated from a nitrogen-bridged dimer precursor reacted with alkenes to form cyclic organosilicon compounds.

Report

(3 results)
  • 2011 Annual Research Report   Final Research Report ( PDF )
  • 2010 Annual Research Report
  • Research Products

    (16 results)

All 2012 2011 2010 Other

All Journal Article (4 results) (of which Peer Reviewed: 4 results) Presentation (11 results) Remarks (1 results)

  • [Journal Article] New catalyst systems for iron-catalyzed hydrosilane reduction of carboxamides2011

    • Author(s)
      H. Tsutsumi, Y. Suanda, H. Nagashima
    • Journal Title

      Chem. Commun

      Volume: 47 Pages: 6581-6583

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] New catalyst systems for iron-catalyzed hydrosilane reduction of carboxamides2011

    • Author(s)
      Hironori Tsutsumi, Yusuke Sunada, Hideo Nagashima
    • Journal Title

      Chemical Communications

      Volume: 47 Issue: 23 Pages: 6581-6583

    • DOI

      10.1039/c1cc10636h

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] "Half-Sandwich(η6-Arene) iron(II) Dinitrogen Complexes Bearing a DisilaferracycleSkeleton as a Precursor for Double Silylation of Ethylene and Alkynes2010

    • Author(s)
      Y. Sunada, T. Imaoka, H. Nagashima
    • Journal Title

      "Half-Sandwich(η6-Arene) iron(II) Dinitrogen Complexes Bearing a DisilaferracycleSkeleton as a Precursor for Double Silylation of Ethylene and Alkynes

      Volume: 29 Pages: 6157-6160

    • URL

      http://dx.doi.org/10.1021/om100889w

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Half-Sandwich (η^6-Arene)iron(II) Dinitrogen Complexes Bearing a Disilaferracycle Skeleton as a Precursor for Double Silylation of Ethylene and Alkynes2010

    • Author(s)
      H.Nagashima, et al
    • Journal Title

      Organometallics

      Volume: 29 Pages: 6157-6160

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] トリアザシクロノナン配位子を有する単核鉄錯体の合成と原子移動型ラジカル重合反応活性の相関2012

    • Author(s)
      中西崇一朗・砂田祐輔・河村充展・甲斐英知・笹本茜・小池展行・早川均・金仁華・永島英夫
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2012-03-26
    • Related Report
      2011 Annual Research Report 2011 Final Research Report
  • [Presentation] 高活性鉄7核カルボニル錯体によるアミド化合物の還元反応2011

    • Author(s)
      堤大典、砂田祐輔、永島英夫
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      愛知
    • Year and Date
      2011-09-08
    • Related Report
      2011 Annual Research Report 2011 Final Research Report
  • [Presentation] ジシラメタラサイクル骨格を有する(η6-arene) Fe(IV)ジヒドリド錯体の合成とarene交換反応2011

    • Author(s)
      今岡剛、砂田祐輔、永島英夫
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-28
    • Related Report
      2011 Final Research Report
  • [Presentation] ジシラメタラサイクル骨格を有する(η^6-arene)Fe(IV)ジヒドリド錯体の合成とarene交換反応2011

    • Author(s)
      砂田祐輔、今岡剛、永島英夫
    • Organizer
      日本化学会 第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-28
    • Related Report
      2010 Annual Research Report
  • [Presentation] 高活性鉄7核カルボニル錯体によるアミド化合物の還元反応2011

    • Author(s)
      堤大典、砂田祐輔、永島英夫
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-27
    • Related Report
      2011 Final Research Report
  • [Presentation] 高活性鉄7核カルボニル錯体によるアミド化合物の還元反応2011

    • Author(s)
      堤大典、砂田祐輔、永島英夫
    • Organizer
      日本化学会 第91春季年会
    • Place of Presentation
      神奈川
    • Year and Date
      2011-03-27
    • Related Report
      2010 Annual Research Report
  • [Presentation] Dinuclear half-sandwich(η6-arene) Fe(II) dinitrogen complexes having a disilametallacycle skeleton2010

    • Author(s)
      Yusuke Sunada, Tsuyoshi Imaoka, Hideo Nagashima
    • Organizer
      The International Chemical Congress of Pacific Basin Societies(Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2010-12-16
    • Related Report
      2011 Final Research Report
  • [Presentation] Dinuclear half-sandwich (η^6-arene)Fe(II) dinitrogen complexes having a disilametal lacycle skeleton2010

    • Author(s)
      Yusuke Sunada, Tsuyoshi Imaoka, Hideo Nagashima
    • Organizer
      The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2010-12-16
    • Related Report
      2010 Annual Research Report
  • [Presentation] Hydrosilane Reduction of Tertiary Carboxamides by Iron Carbonyl Catalysts2010

    • Author(s)
      Yusuke Sunada, Tsuyoshi Imaoka, Hideo Nagashima
    • Organizer
      24th International Conference on Organometallic Chemistry
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2010-07-22
    • Related Report
      2011 Final Research Report 2010 Annual Research Report
  • [Presentation] Yusuke Sunada, Hiroko Kawakami, Tsuyoshi Imaoka, Hideo Nagashima2010

    • Author(s)
      Yusuke Sunada, Hiroko Kawakami, Tsuyoshi Imaoka, Hideo Nagashima
    • Organizer
      tallic Chemistry
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2010-07-22
    • Related Report
      2011 Final Research Report
  • [Presentation] (η^6-arene)Fe(II) Dinitrogen Complexes Bearing A Disilametallacycle Skeleton : Synthesis, Structure, and Thier Unique Reactivities2010

    • Author(s)
      Yusuke Sunada, Tsuyoshi Imaoka, Hideo Nagashima
    • Organizer
      24th International Conference on Organometallic Chemistry
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2010-07-22
    • Related Report
      2010 Annual Research Report
  • [Remarks]

    • URL

      http://www.cm.kyushu-u.ac.jp/dv04/dv04j.html

    • Related Report
      2011 Final Research Report

URL: 

Published: 2010-08-23   Modified: 2016-04-21  

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