• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

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

Nagashima Hideo  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 2021)
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金属 / 強配位子場配位子 / 錯体設計 / 触媒反応 / 反応機構 / ヒドロシリル化 / カルボニル化合物 / 還元反応 / 3d遷移金属 / 均一系触媒 / 有機・高分子合成 / 低スピン設計 / 錯体 / 触媒 / 有機合成 / 高分子合成 / 錯体触媒 / 機能性分子開発 / 鉄 / ベースメタル / 有機金属錯体
Outline of Final Research Achievements

Homogeneous catalysis is a key technology for environmentally benign chemical processes. Precious metal complexes have been widely used as the catalyst; however, practical processes using iron and other 3d metal catalysts are important to take part in SDGs through element strategy initiative. We have proposed the catalyst design of iron and 3d metals by appropriate choice of structures of complexes and use of strong field ligands. In this study, highly efficient hydrosilylation of alkenes and carbonyl compounds were experimentally achieved according to this proposal, and mechanisms were elucidated by DFT calculations. The results not only make the present concept for the catalyst design of iron and 3d metals be widely accepted but also provide practical processes for hydrosilylation reactions; one of them are useful for production of silicones even in industrial processes.

Academic Significance and Societal Importance of the Research Achievements

均一系触媒において、触媒金属は貴金属が一般的に用いられるが、元素戦略によるSDGsの実現が求められる中で、触媒金属の安価で地殻存在量が多い鉄および3d金属へのシフトが重要な課題となっている。本研究では、3d金属触媒開発の鍵を、高スピンになりやすい3d金属の低スピン化であると提案し、それを実現することにより、アルケンやカルボニル化合物の高効率的ヒドロシリル化反応を達成し、さらにその機構を理論的に解明することを通じて、学術界に新しい触媒設計概念を提供した点で優れた学術的意義を持つ。一方、高効率的ヒドロシリル化反応は、実験室的にも工業的にも実用性を持つことから、社会に与えたインパクトは大きい。

Report

(4 results)
  • 2021 Final Research Report ( PDF )
  • 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, 2432-5953
    • 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

      The Journal of Organic Chemistry

      Volume: 84 Issue: 13 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

      The Journal of Organic Chemistry

      Volume: 84 Issue: 23 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 Issue: 4

    • 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 Issue: 17 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 Issue: 79 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 Issue: 1 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

URL: 

Published: 2018-04-23   Modified: 2023-01-30  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi