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Development of precisely designed metalloligands for new transition metal catalysis

Research Project

Project/Area Number 17H03019
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

Takaya Jun  東京工業大学, 理学院, 准教授 (60401535)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000)
Fiscal Year 2019: ¥7,670,000 (Direct Cost: ¥5,900,000、Indirect Cost: ¥1,770,000)
Fiscal Year 2018: ¥8,060,000 (Direct Cost: ¥6,200,000、Indirect Cost: ¥1,860,000)
Fiscal Year 2017: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords有機合成化学 / 有機金属化学 / 錯体化学 / 合成化学
Outline of Final Research Achievements

We have successfully synthesized a series of palladium complexes having a Z-type, group 13 metalloligand utilizing 6,6''-bis(phosphino)-2,2':6',2''-terpyridine derivatives as an efficient scaffold for M-E bonds (E = Al, Ga, In). Systematic investigation revealed unique characteristics of the Al-metalloligand in both structure and reactivity, which exhibited the highest catalytic activity for hydrosilylation of CO2 ever reported (TOF = 19300 h-1). We have also achieved synthesis of an Ir complex having a pincer-type gallylene ligand through the complexation-induced reduction of GaIII by IrI utilizing the N,P-multidentate ligand. The pincer-type structure enabled various reactions at Ir with keeping the gallylene ligand intact. Furthermore, we also demonstrated that the Ga-Rh complex can be an efficient catalyst for hydrosilylation of nitriles to imine oxidation level. This is a highly useful method for the synthesis of oximes from nitriles.

Academic Significance and Societal Importance of the Research Achievements

本研究では,独自に開発した遷移金属二核錯体が,二酸化炭素の超効率的固定化反応などにおける超効率的触媒として機能することを明らかにした。これは,省資源・省エネルギー型の有用物質合成を実現するものとして大きな意義を持つ。

Report

(4 results)
  • 2020 Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • Research Products

    (30 results)

All 2021 2020 2019 2018 2017

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Open Access: 1 results) Presentation (22 results) (of which Int'l Joint Research: 6 results,  Invited: 2 results)

  • [Journal Article] Catalysis using transition metal complexes featuring main group metal and metalloid compounds as supporting ligands2021

    • Author(s)
      Takaya Jun
    • Journal Title

      Chemical Science

      Volume: 12 Issue: 6 Pages: 1964-1981

    • DOI

      10.1039/d0sc04238b

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ruthenium-catalyzed regio- and site-selective ortho C?H borylation of phenol derivatives2020

    • Author(s)
      Homma Yuki、Fukuda Kazuishi、Iwasawa Nobuharu、Takaya Jun
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 73 Pages: 10710-10713

    • DOI

      10.1039/d0cc02889d

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Chemoselective Hydrosilylation of Nitriles to an Imine Oxidation Level Enabled by a Pincer-type Group 13 Metallylene Ligand2020

    • Author(s)
      Takaya Jun、Ogawa Koki、Nakaya Ryota、Iwasawa Nobuharu
    • Journal Title

      ACS Catalysis

      Volume: 10 Issue: 20 Pages: 12223-12228

    • DOI

      10.1021/acscatal.0c02779

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] ピンサー型錯体を用いる有機合成反応の新展開2020

    • Author(s)
      鷹谷 絢,岩澤伸治
    • Journal Title

      カレントレビュー 高機能性金属錯体が拓く触媒科学

      Volume: 37 Pages: 40-52

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-catalyzed ortho C-H Borylation of Arylphosphines: A Powerful Tool for Late-Stage Modification of Phosphorus Compounds2019

    • Author(s)
      K. Fukuda, N. Iwasawa, J. Takaya
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 58 Issue: 9 Pages: 2850-2853

    • DOI

      10.1002/anie.201813278

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Structure, and Reactivity of a Mononuclear η2-(Ge-H)palladium(0) Complex Bearing a PGeP-Pincer Type Ligand: Reactivity Differences Between Silicon and Germanium2018

    • Author(s)
      J. Takaya, N. Iwasawa
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2018 Issue: 46 Pages: 5012-5018

    • DOI

      10.1002/ejic.201801257

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation2017

    • Author(s)
      Imayoshi Ryuji、Nakajima Kazunari、Takaya Jun、Iwasawa Nobuharu、Nishibayashi Yoshiaki
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2017 Issue: 32 Pages: 3769-3778

    • DOI

      10.1002/ejic.201700569

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Aluminum-Metalloligand in Hydrosilylation of CO22017

    • Author(s)
      Takaya Jun、Iwasawa Nobuharu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 17 Pages: 6074-6077

    • DOI

      10.1021/jacs.7b02553

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] 金属-金属結合の触媒機能の開拓2020

    • Author(s)
      鷹谷 絢
    • Organizer
      オンライン公開シンポジウム ー革新的触媒と反応制御の今後ー
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] メタロリガンド ~どう作るか?何ができるか?~2020

    • Author(s)
      鷹谷 絢
    • Organizer
      第126回フロンティア材料研究所学術講演会 「有機・錯体・無機材料の構造と機能」
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 13 族金属を配位子とする Cp ロジウムならびにイリジウム錯体の合成と反応2019

    • Author(s)
      Ryosuke Yamada, Nobuharu Iwasawa, Jun Takaya
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 低原子価 13 族金属含有ピンサー型配位子を持つ 9 族金属ヒドリド錯体の合成と反応2019

    • Author(s)
      Mayuko Hoshino, Kanako Ueki, Jun Takaya, Nobuharu Iwasawa
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 高周期 14 族元素含有ピンサー型配位子を持つ鉄-亜鉛複核錯体の合成と反応2019

    • Author(s)
      Kai Takizawa, Norio Miura, Tatsuyoshi Ito, Jun Takaya, Nobuharu Iwasawa
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] ルテニウム触媒によるアリールホスフィンのオルト位 C-H 結 合ホウ素化反応2019

    • Author(s)
      Kazuishi Fukuda, Nobuharu Iwasawa, Jun Takaya
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Ru-Catalyzed C?H Borylation of Arylphosphines: A Powerful Tool for Modification of Phosphine Ligands2018

    • Author(s)
      Kazuishi Fukuda, Ryosuke Yamada, Nobuharu Iwasawa, Jun Takaya
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Metalloligands2018

    • Author(s)
      Jun Takaya
    • Organizer
      FHI-JST Joint Symposium
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] PSiP-Platinum Complexes-Promoted C-H Bond Activation and Transformation of Benzene2018

    • Author(s)
      Ryota Nakaya, Jun Takaya, Nobuharu Iwasawa
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Group 13 Metalloligands2018

    • Author(s)
      Jun Takaya
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Group 13 Metalloligands2018

    • Author(s)
      Jun Takaya
    • Organizer
      4th International Conference on Organometallic and Catalysis 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Metalloligands2018

    • Author(s)
      Jun Takaya
    • Organizer
      The 1st Sino-Japanese Symposium on Catalysis for Precision Synthesis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 金属ハイブリッド触媒 ~どう作るか? 何ができるか?~2018

    • Author(s)
      Jun Takaya
    • Organizer
      第8回 CSJ化学フェスタ2018 コラボレーション企画 「1+1は3?」ハイブリッド触媒が紡ぎ出す新反応化学
    • Related Report
      2018 Annual Research Report
  • [Presentation] Ruthenium-Catalyzed C?H Borylation of Aryl Phosphines2018

    • Author(s)
      Kazuishi Fukuda, Ryosuke Yamada, Nobuharu Iwasawa, Jun Takaya
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Highly Efficient Hydrosilylation Reactions Catalyzed by Al?Pd Bimetallic Complexes2018

    • Author(s)
      Jun Takaya, Akira Shiozuka, Narumasa Saito, Nobuharu Iwasawa
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Multifunctional Ligands2018

    • Author(s)
      Jun Takaya
    • Organizer
      The 2nd Base Metal Catalysis Symposium ~After Discussion~
    • Related Report
      2017 Annual Research Report
  • [Presentation] PGeP-ピンサー型配位子を有するレニウム錯体によるアレンの ヒドロホウ素化反応2018

    • Author(s)
      村上桃香・杉本忠大・鷹谷 絢・ 岩澤伸治
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 高周期 14 族元素含有ピンサー型配位子を持つ白金錯体の合成と反応2018

    • Author(s)
      中屋良太・鷹谷 絢・岩澤伸治
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Al-Pd 二核錯体を触媒とするヒドロシリル化反応の開発2018

    • Author(s)
      塩塚 朗・斉藤成将・鷹谷 絢・岩澤伸治
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 13族金属含有ピンサー型配位子を持つイリジウム 錯体の合成とその構造と反応性族金属含有ピンサー型配位子を持つイリジウム 錯体の合成とその構造と反応性2017

    • Author(s)
      斉藤 成将・鷹谷 絢・岩澤 伸治
    • Organizer
      第 64 回 有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Al-Metalloligand in Hydrosilylation of CO22017

    • Author(s)
      Jun Takaya and Nobuharu Iwasawa
    • Organizer
      Organometallic Chemistry Directed Toward Organic Synthesis (OMCOS19)
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis, Structure and Reactivity of Iridium Complexes Having a Gallium-Containing Pincer Type Ligand2017

    • Author(s)
      Narimasa Saito, Jun Takaya, and Nobuharu Iwasawa
    • Organizer
      Organometallic Chemistry Directed Toward Organic Synthesis (OMCOS19)
    • Related Report
      2017 Annual Research Report

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Published: 2017-04-28   Modified: 2022-01-27  

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