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Development of Multimetallic Catalysts Composed of Redox-Active Transition Metals

Research Project

Project/Area Number 20H02732
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 InstitutionTokyo Institute of Technology

Principal Investigator

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

Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000)
Fiscal Year 2022: ¥7,670,000 (Direct Cost: ¥5,900,000、Indirect Cost: ¥1,770,000)
Fiscal Year 2021: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2020: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords有機合成化学 / 有機合成
Outline of Research at the Start

本研究では「金属間協働作用の戦略的利用を可能にする多核遷移金属錯体触媒の精密設計と機能開拓」に取り組む。これにより,従来の単核金属では実現困難な「二酸化炭素や水などの普遍小分子を合成素子とする新しい分子変換反応」や「単純飽和炭化水素のsp3C-H結合変換反応」といった高難度分子変換反応を実現する。

Outline of Final Research Achievements

New Ru-Pd heterobimetallic complexes were synthesized and structurally characterized utilizing 6,6''-bis(phosphino)-2,2':6',2''-terpyridine as a scaffold for the metal-metal bond. The dicationic Ru-Pd complex was found to exhibit high catalytic activity as a photocatalyst for photochemical re-duction of CO2 to CO under visible light irradiation. This study established a new design of transition metal catalysts that tune photoredox catalysis with metalloligands.

Academic Significance and Societal Importance of the Research Achievements

2つの異なる遷移金属からなる異種金属二核錯体の効率的合成手法を確立すると共に,有機合成反応開発における触媒としての有用性と実用性を実証したものとして大きな意義を持つ。

Report

(4 results)
  • 2023 Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • Research Products

    (25 results)

All 2024 2023 2022 2021 2020

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Open Access: 4 results) Presentation (13 results) (of which Int'l Joint Research: 1 results,  Invited: 6 results)

  • [Journal Article] Tuning Photoredox Catalysis of Ruthenium with Palladium: Synthesis of Heterobimetallic Ru-Pd Complexes That Enable Efficient Photochemical Reduction of CO<sub>2</sub>2024

    • Author(s)
      Yang Siteng、Morita Yuto、Nakamura Yuta、Iwasawa Nobuharu、Takaya Jun
    • Journal Title

      Journal of the American Chemical Society

      Volume: - Issue: 18 Pages: 12288-12293

    • DOI

      10.1021/jacs.3c14338

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Methylene Insertion into Nitrogen‐Heteroatom Single Bonds of 1,2‐Azoles via a Zinc Carbenoid: An Alternative Tool for Skeletal Editing2023

    • Author(s)
      Tsuda Masato、Morita Taiki、Morita Yuto、Takaya Jun、Nakamura Hiroyuki
    • Journal Title

      Advanced Science

      Volume: 11 Issue: 10 Pages: 2307563-2307563

    • DOI

      10.1002/advs.202307563

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Reversible Boron‐Insertion into Aromatic C-C Bonds2023

    • Author(s)
      Kuroki Kaito、Ito Tatsuyoshi、Takaya Jun
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 62 Issue: 48

    • DOI

      10.1002/anie.202312980

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Origin of Reactivity Difference between Phosphines and Phosphinites in Ru-Catalyzed Phosphorus-Directed sp2C-H Borylation: Mechanistic Study and Improvement of Reaction Conditions2023

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

      Bulletin of the Chemical Society of Japan

      Volume: 96 Issue: 9 Pages: 842-848

    • DOI

      10.1246/bcsj.20230111

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Merging the Norrish type I reaction and transition metal catalysis: photo- and Rh-promoted borylation of C-C σ-bonds of aryl ketone2023

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

      Chemical Science

      Volume: 14 Issue: 8 Pages: 1960-1965

    • DOI

      10.1039/d2sc06801j

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photo-promoted Skeletal Rearrangement of o-Anisyldimesitylborane Involving C-H/C-O/C-B Bond Cleavage2022

    • Author(s)
      K. Hirai, Y. Homma, T. Ito, N. Iwasawa, J. Takaya*
    • Journal Title

      Chemistry Letters

      Volume: - Issue: 5 Pages: 570-573

    • DOI

      10.1246/cl.220106

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile Synthesis and Utilization of Bis(o-phosphinophenyl)zinc as Isolable PZnP-pincer Ligands Enabled by Boron-Zinc Double Transmetallation2022

    • Author(s)
      Fukuda Kazuishi、Harada Takuma、Iwasawa Nobuharu、Takaya Jun
    • Journal Title

      Dalton Transactions

      Volume: - Issue: 18 Pages: 7035-7039

    • DOI

      10.1039/d2dt01222g

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [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
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [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
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photo‐promoted Skeletal Rearrangement of Phosphine?Borane Frustrated Lewis Pairs Involving Cleavage of Unstrained C?C σ‐Bonds2020

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

      Angewandte Chemie International Edition

      Volume: 59 Issue: 29 Pages: 11913-11917

    • DOI

      10.1002/anie.202004444

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [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
      2020 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
      2020 Annual Research Report
    • Peer Reviewed
  • [Presentation] 新しい分子触媒作用と反応性の開拓2024

    • Author(s)
      鷹谷 絢
    • Organizer
      日本化学会 第104春季年会(2024)
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 協働触媒による不活性結合・不活性分子変換反応の開発2023

    • Author(s)
      鷹谷 絢
    • Organizer
      さきがけ「革新的触媒の科学と創製」第1回領域研究会
    • Related Report
      2022 Annual Research Report
  • [Presentation] ハイブリッド化を鍵とする新触媒・新反応の開発2023

    • Author(s)
      鷹谷 絢
    • Organizer
      第55回有機金属若手の会夏の学校
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Merging Two Transition Metals/Two Reactions for Transformation of Unreactive Bonds and Molecules2023

    • Author(s)
      Jun Takaya
    • Organizer
      7th UK-Japan Catalysis Meeting ~Contemporary Catalysis for a Sustainable World~
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Ambiphilicホスフィン-ボロン化合物の光/熱による可逆な芳香環分解反応2022

    • Author(s)
      黒木 海都,伊藤 龍好,岩澤 伸治,鷹谷 絢
    • Organizer
      日本化学会 第102春季年会(2022)
    • Related Report
      2021 Annual Research Report
  • [Presentation] 複数のケイ素配位子をもつCpレニウムヒドリド錯体の合成・構造・反応性2022

    • Author(s)
      森田 悠斗,伊藤 龍好,岩澤 伸治,鷹谷 絢
    • Organizer
      日本化学会 第102春季年会(2022)
    • Related Report
      2021 Annual Research Report
  • [Presentation] アリールケトンの炭素-炭素sigma-結合ホウ素化反応2022

    • Author(s)
      藤巻 友樹,岩澤 伸治,鷹谷 絢
    • Organizer
      日本化学会 第102春季年会(2022)
    • Related Report
      2021 Annual Research Report
  • [Presentation] 金属複合触媒の創製と機能開拓2021

    • Author(s)
      鷹谷絢
    • Organizer
      第48回オルガノメタリックセミナー「効率的分子変換のフロンティア」
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] フラストレイテッドルイスペアの光骨格転位反応2021

    • Author(s)
      伊藤龍好,平井宏典,本間優生,岩澤伸治,鷹谷絢
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ルテニウム-パラジウム二核錯体を光触媒とするを用いた二酸化炭素の光還元反応2021

    • Author(s)
      楊 斯騰,小川功喜,鷹谷絢,岩澤伸治
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Ambiphilicホスフィン-ボラン化合物の光骨格転位反応による1,4-ホスファボリン誘導体の効率的合成2021

    • Author(s)
      伊藤龍好、平井宏典、本間優生、岩澤伸治、鷹谷絢
    • Organizer
      第 118 回有機合成シンポジウム
    • Related Report
      2021 Annual Research Report
  • [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
      2020 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
      2020 Annual Research Report
    • Invited

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Published: 2020-04-28   Modified: 2025-01-30  

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