Development of Multimetallic Catalysts Composed of Redox-Active Transition Metals

• Project/Area Number: 20H02732
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Tokyo 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: ¥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。

Research Products

• [Journal Article] Tuning Photoredox Catalysis of Ruthenium with Palladium: Synthesis of Heterobimetallic Ru-Pd Complexes That Enable Efficient Photochemical Reduction of CO₂ (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
  • Peer Reviewed
• [Journal Article] Methylene Insertion into Nitrogen‐Heteroatom Single Bonds of 1,2‐Azoles via a Zinc Carbenoid: An Alternative Tool for Skeletal Editing (2023)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Reversible Boron‐Insertion into Aromatic C-C Bonds (2023)
  • Author(s): Kuroki Kaito、Ito Tatsuyoshi、Takaya Jun
  • Journal Title: Angewandte Chemie International Edition Volume: 62 Issue: 48
  • DOI: 10.1002/anie.202312980
  • 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 Conditions (2023)
  • 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
  • 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 ketone (2023)
  • Author(s): Fujimaki Yuki、Iwasawa Nobuharu、Takaya Jun
  • Journal Title: Chemical Science Volume: 14 Issue: 8 Pages: 1960-1965
  • DOI: 10.1039/d2sc06801j
  • Peer Reviewed / Open Access
• [Journal Article] Photo-promoted Skeletal Rearrangement of o-Anisyldimesitylborane Involving C-H/C-O/C-B Bond Cleavage (2022)
  • 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
  • Peer Reviewed
• [Journal Article] Facile Synthesis and Utilization of Bis(o-phosphinophenyl)zinc as Isolable PZnP-pincer Ligands Enabled by Boron-Zinc Double Transmetallation (2022)
  • Author(s): Fukuda Kazuishi、Harada Takuma、Iwasawa Nobuharu、Takaya Jun
  • Journal Title: Dalton Transactions Volume: - Issue: 18 Pages: 7035-7039
  • DOI: 10.1039/d2dt01222g
  • Peer Reviewed
• [Journal Article] Catalysis using transition metal complexes featuring main group metal and metalloid compounds as supporting ligands (2021)
  • Author(s): Takaya Jun
  • Journal Title: Chemical Science Volume: 12 Issue: 6 Pages: 1964-1981
  • DOI: 10.1039/d0sc04238b
  • 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
  • Peer Reviewed
• [Journal Article] Photo‐promoted Skeletal Rearrangement of Phosphine?Borane Frustrated Lewis Pairs Involving Cleavage of Unstrained C?C σ‐Bonds (2020)
  • 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
  • Peer Reviewed
• [Journal Article] Ruthenium-catalyzed regio- and site-selective ortho C?H borylation of phenol derivatives (2020)
  • 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
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Chemoselective Hydrosilylation of Nitriles to an Imine Oxidation Level Enabled by a Pincer-type Group 13 Metallylene Ligand (2020)
  • 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
  • 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）
  • 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
• [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
  • Invited
• [Presentation] Merging Two Transition Metals/Two Reactions for Transformation of Unreactive Bonds and Molecules (2023)
  • Author(s): Jun Takaya
  • Organizer: 7th UK-Japan Catalysis Meeting ~Contemporary Catalysis for a Sustainable World~
  • 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)
• [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)
• [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)
• [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」
  • 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
• [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
• [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
• [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
  • 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」
  • Invited