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Development of highly efficient non-precious metal catalysts by low-spin design of iron and other 3d metals.

Research Project

Project/Area Number 18H01980
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionKyushu University

Principal Investigator

永島 英夫  九州大学, グリーンテクノロジー研究教育センター, 特任教授 (50159076)

Co-Investigator(Kenkyū-buntansha) 田原 淳士  東北大学, 学際科学フロンティア研究所, 助教 (50713145)
Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥15,730,000 (Direct Cost: ¥12,100,000、Indirect Cost: ¥3,630,000)
Fiscal Year 2020: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2019: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2018: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
Keywords3d遷移金属 / 均一系触媒 / 有機・高分子合成 / 低スピン設計 / ヒドロシリル化 / 錯体 / 触媒 / 有機合成 / 高分子合成 / 錯体触媒 / 触媒反応 / 反応機構 / 機能性分子開発 / 3d金属 / 強配位子場配位子 / 錯体設計 / カルボニル化合物 / 還元反応 / 鉄 / ベースメタル / 有機金属錯体
Outline of Annual Research Achievements

本研究では、均一系触媒反応の元素戦略の一環として、「錯体の幾何構造と配位子を適切に設計し、すべての触媒活性種を低スピン状態に制御する」という考え方を、錯体化学、有機合成化学、計算科学、機能分子開発の4段階で具現化し、貴金属触媒代替反応を鉄および3d金属触媒反応で実現する。2018年度に、イソシアニドを配位子とした低スピン鉄、コバルト錯体の合成、解析、素反応過程の解明と、不飽和化合物の触媒的ヒドロシリル化反応と水素化を達成した。2019年度は、低スピン鉄、コバルトーイソシアニド活性種を、新規で構造が明確な鉄、コバルトアルコキシド錯体を前駆体に用いたアルケンのヒドロシリル化反応を実現するとともに、触媒的ヒドロシリル化について、鉄、コバルトから、マンガン、ニッケル触媒に拡張した。2020年度は、触媒活性種の低スピン設計の代表例である一酸化炭素またはイソシアニドを配位子とするコバルト錯体のアルケンのヒドロシリル化触媒の反応機構を計算科学で明らかにし、実験と計算結果を比較検討した。とくに、コバルトカルボニル触媒を用いるヒドロシリル化反応の機構論争に重要な示唆を与える結果を得た。3d金属と比較検討するため、貴金属であるロジウム触媒を用いる水中での不斉ラジカル付加反応の鉄や銅触媒との比較検討をおこなったほか、イリジウムの触媒機能を開拓し、ホール輸送機能を持つエナミンの合成法の確立、高効率的カルボニル還元反応の開発を行うとともに、イリジウムの3d金属代替についての可能性を検討した。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Report

(3 results)
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report

Research Products

(33 results)

All 2022 2021 2020 2019 2018 Other

All Int'l Joint Research (1 results) Journal Article (9 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 9 results,  Open Access: 3 results) Presentation (18 results) (of which Int'l Joint Research: 8 results,  Invited: 7 results) Book (1 results) Patent(Industrial Property Rights) (4 results) (of which Overseas: 3 results)

  • [Int'l Joint Research] Ajou University(韓国)

    • Related Report
      2018 Annual Research Report
  • [Journal Article] 「1+1>2」~有機金属触媒反応における複数の元素の相乗効果~2022

    • Author(s)
      永島英夫
    • Journal Title

      Organometallic News

      Volume: 2022 Pages: 2-7

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Asymmetric Kharasch Addition “On Water” Catalyzed by “RhCl[(–)-DIOP]” Species2021

    • Author(s)
      Atsushi Tahara, Hikaru Takao, Hiroshi Furuno, Hideo Nagashima
    • Journal Title

      Evergreen

      Volume: 8 Issue: 3 Pages: 535-543

    • DOI

      10.5109/4491639

    • NAID

      120007151385

    • ISSN
      2189-0420
    • URL

      http://hdl.handle.net/2324/4491639

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane2019

    • Author(s)
      Zhao Liming、Nakatani Naoki、Sunada Yusuke、Nagashima Hideo、Hasegawa Jun-ya
    • Journal Title

      Journal of Organic Chemistry

      Volume: 84 Pages: 8552-8561

    • DOI

      10.1021/acs.joc.9b00959

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Donor?Acceptor π-Conjugated Enamines: Functional Group-Compatible Synthesis from Amides and Their Photoabsorption and Photoluminescence Properties2019

    • Author(s)
      Tahara Atsushi、Kitahara Ikumi、Sakata Daichi、Kuninobu Yoichiro、Nagashima Hideo
    • Journal Title

      Journal of Organic Chemistry

      Volume: 84 Pages: 15236-15254

    • DOI

      10.1021/acs.joc.9b02267

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 原子移動ラジカル重合用鉄触媒設計法2019

    • Author(s)
      永島英夫
    • Journal Title

      触媒

      Volume: 61 Pages: 124-134

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] MAO-free and extremely active catalytic system for ethylene tetramerization2019

    • Author(s)
      Kim Tae Hee、Lee Hyun Mo、Park Hee Soo、Kim Sung Dong、Kwon Su Jin、Tahara Atsushi、Nagashima Hideo、Lee Bun Yeoul
    • Journal Title

      Applied Organometallic Chemistry

      Volume: 33

    • DOI

      10.1002/aoc.4829

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes2018

    • Author(s)
      A. Sanagawa, H. Ngaashima
    • Journal Title

      Organometallics

      Volume: 37 Pages: 2859-2871

    • DOI

      10.1021/acs.organomet.8b00389

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Remarkably high catalyst efficiency of a disilaruthenacyclic complex for hydrosilane reduction of carbonyl compounds2018

    • Author(s)
      Tahara Atsushi、Sunada Yusuke、Takeshita Takashi、Inoue Ryoko、Nagashima Hideo
    • Journal Title

      Chemical Communications

      Volume: 54 Pages: 11192-11195

    • DOI

      10.1039/c8cc04780d

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrosilane Reduction of Nitriles to Primary Amines by CobaltーIsocyanide Catalysts2018

    • Author(s)
      A. Sanagawa, H. Nagashima
    • Journal Title

      Organic Letters

      Volume: 21 Pages: 287-291

    • DOI

      10.1021/acs.orglett.8b03736

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] 「1+1>2」2021

    • Author(s)
      永島英夫
    • Organizer
      近畿化学協会有機金属部会2021年度第2回例会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] Base metal catalyst systems for effective hydrosilylation reactions2021

    • Author(s)
      Nagashima, H.; Tachikawa, H.; Ninomiya, S.; Sanagawa, A.
    • Organizer
      ISOS-2021, The 19th International Symposium on Silicon Chemistry
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Activation of H-H and H-Si bonds by transition metal-silicon linkage,2020

    • Author(s)
      Hideo Nagashima
    • Organizer
      The 3rd IRCCS - The 2nd Reaction Infography Joint International Symposium: “Reaction Imaging Meets Materials Science”, January 31-February 1, 2020, Nagoya, Japan.
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 制御されたラジカル重合用Fe(II)錯体触媒の設計2020

    • Author(s)
      永島英夫
    • Organizer
      制御されたラジカル重合用Fe(II)錯体触媒の設計, 永島英夫, 九州錯体化学懇談会第259回例会, 2019年7月12-13日, 長崎
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Ir-catalyzed Syntheses of Donor-Acceptor pai-Conjugated Enamines and Their Photoluminescence Properties.2020

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      日本化学会 第 100 回 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 金属ジアリール錯体とアルコールまたはカルボン酸との反応による新規鉄およびコバルト錯体の合成およびアルケンの触媒的ヒドロシリル化2020

    • Author(s)
      二宮 俊吾, 田原 淳士, 永島 英夫
    • Organizer
      日本化学会 第 100 回 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Hydrosilane Reduction of Tertiary Amides: Controlling of the Product Selectivity by Transition Metal Catalysts2020

    • Author(s)
      立川 晴紀, 真川 敦嗣, 永島 英夫
    • Organizer
      日本化学会 第 100 回 春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Photoabsorption and Photoluminescence Properties of Donor-Acceptor pai-Conjugated Enamines and Their Additive Effects with B(C6F5)32020

    • Author(s)
      Atsushi Tahara, Daichi Sakata, Ikumi Kitahara, Yoichiro Kuninobu, Hideo Nagashima
    • Organizer
      IRCCS the 3rd International Symposium, Nagoya University, Aichi (Japan), January 31-February 1 (2020).
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Environmentally Friendly Polymer Synthesis by Transition Metal Catalysts,2019

    • Author(s)
      Hideo Nagashima
    • Organizer
      The International Polymer Conference of Thailand (PCT-9), June 13-14, 2019, Bangkok, Thailand
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] イリジウム触媒を用いたアミドの化学選択的ヒドロシラン還元による D-A 型 共役エナミンの合成2019

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      統合物質創成科学研究推進機構 (IRCCS) 第5回国内シンポジウム, 北海道大学 (北海道), 2019 年 11 月 18-19 日
    • Related Report
      2019 Annual Research Report
  • [Presentation] イリジウム触媒を用いたアミドの化学選択的ヒドロシラン還元による D-A 型 pai 共役エナミンの合成2019

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      第23回ケイ素化学協会シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] Ir-Catalyzed Chemoselective Hydrosilane Reduction of Carboxamides bearing Electron-Withdrawing Group Leading to the Formation of Donor-Acceptor-Type pai-Conjugated Enamines and Their Photochemical Properties2019

    • Author(s)
      田原 淳士, 北原 いくみ, 坂田 大地, 國信 洋一郎, 永島 英夫
    • Organizer
      近畿化学会 第 66 回 有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 3.Catalytic Hydrogenation Reactions by New Organometallic Catalysts2019

    • Author(s)
      Hideo Nagashima
    • Organizer
      Pure and Applied Chemistry International Conference 2019
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 遷移金属とケイ素の結合がもたらす効率的な触媒反応2018

    • Author(s)
      永島英夫
    • Organizer
      第22回ケイ素科学シンポジウム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 2.Highly Efficient Iridium-catalyzed Reduction of Amides to Enamines with 1,1,3,3-Tetramethyldisiloxane (TMDS): Catalyst design, Mechanisms, and Applications2018

    • Author(s)
      Hideo Nagashima
    • Organizer
      The 18th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Reverse ATRP of St and MMA Catalyzed by Me3TACNFeX3 (X = Cl, Br)2018

    • Author(s)
      Atsushi Tahara, Yuto Ii, Yusuke Sunada, Mitsunobu Kawamura, Hideo Nagashima
    • Organizer
      IRCCS the 2nd International Symposium
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Theoretical Studies for Hydrogenation of Multisubstituted Alkenes Catalyzed by Disilametalla-cycle Complexes Bearing Isocyanide Ligands (M=Fe, Ru)2018

    • Author(s)
      Atsushi Tahara, Yusuke Sunada, Hideo Nagashima
    • Organizer
      6th Japanー;UK Symposium on Asymmetric Catalysis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Reverse Atom Transfer Radical Polymerization of St and MMA by (Me3TACN)FeX3 (X = Cl, Br)2018

    • Author(s)
      田原 淳士, 飯 勇人, 河村 充展, 砂田 祐輔, 永島 英夫
    • Organizer
      第 65 回 有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Book] Hydrosilylation Catalyzed by Base Metals in Hiyama, T.; Oestreich, M. Eds. Organosilicon Chemistry: Novel Approach and Reactions2020

    • Author(s)
      Yusuke Sunada and Hideo Nagashima
    • Total Pages
      22
    • Publisher
      Wiley-VCH
    • ISBN
      9783527344536
    • Related Report
      2019 Annual Research Report
  • [Patent(Industrial Property Rights)] 新規イソシアニド化合物、ホルムアミド化合物及びイソシアニド化合物を用いた有機ケイ素化合物の製造方法2019

    • Inventor(s)
      永島 英夫
    • Industrial Property Rights Holder
      永島 英夫
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2019-166837
    • Filing Date
      2019
    • Related Report
      2019 Annual Research Report
  • [Patent(Industrial Property Rights)] Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction2018

    • Inventor(s)
      Hideo Nagashima
    • Industrial Property Rights Holder
      Hideo Nagashima
    • Industrial Property Rights Type
      特許
    • Filing Date
      2018
    • Related Report
      2018 Annual Research Report
    • Overseas
  • [Patent(Industrial Property Rights)] Method for producing transition metal-isocyanide complex2018

    • Inventor(s)
      Hideo Nagashima
    • Industrial Property Rights Holder
      Hideo Nagashima
    • Industrial Property Rights Type
      特許
    • Filing Date
      2018
    • Related Report
      2018 Annual Research Report
    • Overseas
  • [Patent(Industrial Property Rights)] Enamine compound and use thereof as a donor-acceptor type compound2018

    • Inventor(s)
      Hideo Nagashima
    • Industrial Property Rights Holder
      Hideo Nagashima
    • Industrial Property Rights Type
      特許
    • Filing Date
      2018
    • Related Report
      2018 Annual Research Report
    • Overseas

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Published: 2018-04-23   Modified: 2022-12-28  

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