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Transformation of carbon dioxide enabled by multi-electron transfer originating from sigma-electron acceptor ligand

Research Project

Project/Area Number 18K05151
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionOsaka Prefecture University

Principal Investigator

Kameo Hajime  大阪府立大学, 理学(系)研究科(研究院), 准教授 (50597218)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2020: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywords有機金属錯体 / 配位子 / 触媒化学 / 無機化学 / 錯体化学 / 触媒 / 有機金属化学
Outline of Final Research Achievements

Functions of sigma-electron acceptor (Z-type) ligand have been studied, and their applications including the catalysis have been also developed. Firstly, a novel nickel catalysts bearing a Z-type borane ligand was found to show the catalytic activity for the CO2 reduction leading to methanol. In addition, a new type of metal-ligand cooperation was developed by utilizing a Z-type borane ligand, enabling palladium cross coupling reactions based on an unprecedented reaction mechanism. Further, the cross coupling reactions of fluorosilanes and fluorogermanes were achieved, where the cleavage processes of strong Si-F and Ge-F bonds proceeded through the nucleophilic activation by the sigma-back donation.

Academic Significance and Societal Importance of the Research Achievements

σ電子受容性配位子を鍵とする、新しい機構に基づくカップリング反応を提案できた。この新機構では、求核的な触媒活性種による効率的な基質の活性化が期待できることに加えて、結合形成過程が分子内形式で進行するため、難解な結合形成反応への展開も期待できる。カップリング反応の新しい展開が可能となる結果である。
また、σ逆供与を軸とする求核的な活性化法により、強固な Si-F や Ge-F 結合の切断を軸とする初めての触媒を実現することができた。これらの成果は、有機ケイ素化合物、ゲルマニウム化合物の新しい合成法を提案するのみならず、その知見はケイ素化合物のリサイクル技術の発展にも寄与するものと期待できる。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (25 results)

All 2021 2020 2019 2018 Other

All Int'l Joint Research (3 results) Journal Article (7 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 7 results) Presentation (13 results) (of which Invited: 2 results) Remarks (2 results)

  • [Int'l Joint Research] Universite Toulouse III - Paul Sabatier(フランス)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] University Toulouse III - Paul Sabatier(フランス)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] CNRS/Universit; Paul Sabatier(フランス)

    • Related Report
      2018 Research-status Report
  • [Journal Article] Four-Electron Reduction of Dioxygen on a Metal Surface: Models of Dissociative and Associative Mechanisms in a Homogeneous System2021

    • Author(s)
      Hajime Kameo, Shigeyoshi Sakaki, Yasuhiro Ohki, Naoki Uehara, Takuya Kosukegawa, Hiroharu Suzuki, Toshiro Takao
    • Journal Title

      Inorg. Chem.

      Volume: 60 Issue: 3 Pages: 1550-1560

    • DOI

      10.1021/acs.inorgchem.0c02936

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Counterion Dependence of Dinitrogen Activation and Functionalization by a Diniobium Hydride Anion2020

    • Author(s)
      Suzuki Shoi、Ishida Yutaka、Kameo Hajime、Sakaki Shigeyoshi、Kawaguchi Hiroyuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 32 Pages: 13444-13450

    • DOI

      10.1002/anie.202006039

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fluorosilane Activation by Pd/Ni→Si-F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling2020

    • Author(s)
      Kameo Hajime、Yamamoto Hiroki、Ikeda Koki、Isasa Tomohito、Sakaki Shigeyoshi、Matsuzaka Hiroyuki、Garc?a-Rodeja Yago、Miqueu Karinne、Bourissou Didier
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 33 Pages: 14039-14044

    • DOI

      10.1021/jacs.0c04690

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Experimental and Theoretical Investigation of an SN2-type Pathway for Borate?Fluorine Bond Cleavage by Electron-Rich Late-Transition Metal Complexes2020

    • Author(s)
      Kameo Hajime、Baba Yuki、Sakaki Shigeyoshi、Tanaka Yudai、Matsuzaka Hiroyuki
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Issue: 7 Pages: 4282-4291

    • DOI

      10.1021/acs.inorgchem.9b03053

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Heptacoordinate Structures of Organotin Halides with Three Phosphine Donors: Halogen-Substituent Effect on Geometry2019

    • Author(s)
      Kameo Hajime、Kawamoto Tatsuya、Sakaki Shigeyoshi、Bourissou Didier、Nakazawa Hiroshi
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2019 Issue: 26 Pages: 3045-3052

    • DOI

      10.1002/ejic.201900524

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Modulation of the coordination geometries of NCN and NCNC Rh complexes for ambidextrous chiral catalysts2019

    • Author(s)
      Ito Jun-ichi、Ishihara Takahiro、Fukuoka Takaki、Binti Mat Napi Siti Rokiah、Kameo Hajime、Nishiyama Hisao
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 85 Pages: 12765-12768

    • DOI

      10.1039/c9cc06520b

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Palladium?Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination2019

    • Author(s)
      Kameo Hajime、Yamamoto Jun、Asada Ayaka、Nakazawa Hiroshi、Matsuzaka Hiroyuki、Bourissou Didier
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 52 Pages: 18783-18787

    • DOI

      10.1002/anie.201909675

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] σ 電子受容性 (Z型) 配位子を鍵とする反応開発2021

    • Author(s)
      亀尾 肇
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Anionic Rh(-I) Borane Complexes Featuring Seesaw Geometry2019

    • Author(s)
      Hajime Kameo, Jun Yamamoto, Hiroyuki Matsuzaka
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] パラジウム錯体を用いたケイ素-酸素結合の触媒的アリール化反応の開発2019

    • Author(s)
      北村功樹、亀尾 肇、松坂裕之
    • Organizer
      錯体化学会第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] アニオン性ロジウム(-I)ボラン錯体を用いた脱フッ素化反応2019

    • Author(s)
      田中悠大、亀尾 肇、松坂裕之
    • Organizer
      錯体化学会第69回討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] σ 電子受容性 (Z 型) 配位子を鍵とする反応開発2019

    • Author(s)
      亀尾 肇
    • Organizer
      東京大学化学生命工学専攻 談話会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Ir(I)-Mediated Bond Activation of E-F Bond (E = Si, Ge, Sn): A Key Intermediate Bearing a Z-type Interaction2018

    • Author(s)
      Kameo, H.; Nakazawa, H.; Matsuzaka, H.
    • Organizer
      The 15th International Symposium on Inorganic Ring Systems
    • Related Report
      2018 Research-status Report
  • [Presentation] Geometry of Tetracoordinate Rhodium Complex bearing (Rh→B)10 Electron Configuration2018

    • Author(s)
      Kameo, H.; Yamamoto, J.; Matsuzaka, H.
    • Organizer
      The 43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Research-status Report
  • [Presentation] Palladium-Borane Cooperation: Anionic Palladium(0)-Mediated Bond Activation and Intramolecular Nucleophile Transfer from Borane to Carbon Ligand2018

    • Author(s)
      Kameo, H.; Yamamoto, J.; Matsuzaka, H.
    • Organizer
      The 43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] パラジウム‐ボラン協同効果を鍵とするアニオン性活性種の創成とカップリング反応の開発2018

    • Author(s)
      亀尾 肇・山本潤・浅田彩花・松坂裕之
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] パラジウム-ボラン協同効果を鍵とするクロロアレーン類の脱ハロゲン化反応2018

    • Author(s)
      浅田彩花・亀尾 肇・松坂裕之
    • Organizer
      第45回有機典型元素化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] パラジウムおよびニッケル錯体を用いたSi-F結合の触媒的変換反応の開発2018

    • Author(s)
      井笹智仁・亀尾 肇・松坂裕之
    • Organizer
      第45回有機典型元素化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Catalytic Si-F Bond Activation of Fluorosilanes by Group 10 Transition Metal Complexes2018

    • Author(s)
      Akiyama, T.; Kameo, H.; Matsuzaka, H.
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] パラジウム錯体を用いたケイ素-酸素結合の切断反応の開発2018

    • Author(s)
      北村功樹・亀尾 肇・松坂裕之
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Remarks] The Matsuzaka Research Group

    • URL

      http://www.c.s.osakafu-u.ac.jp/~matuzaka/cluster/j-group.htm

    • Related Report
      2020 Annual Research Report
  • [Remarks] 大阪府立大学 松坂研究室

    • URL

      http://www.c.s.osakafu-u.ac.jp/~matuzaka/cluster/j-group.htm

    • Related Report
      2019 Research-status Report 2018 Research-status Report

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Published: 2018-04-23   Modified: 2022-01-27  

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