Development of Rationally Designed Multimetallic Catalysts

• Project/Area Number: 15KT0059
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Multi-year Fund
• Section: 特設分野
• Research Field: Transition State Control
• 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): 2015-07-10 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000); Fiscal Year 2017: ¥8,320,000 (Direct Cost: ¥6,400,000、Indirect Cost: ¥1,920,000); Fiscal Year 2016: ¥7,670,000 (Direct Cost: ¥5,900,000、Indirect Cost: ¥1,770,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 有機合成化学 / 合成化学

Outline of Final Research Achievements

We have rationally designed and synthesized multimetallic complexes having a metal-metal bond. We also demonstrated these complexes can catalyze efficient reactions of unreactive molecules such as carbon dioxide and clarified their unique catalysis through theoretical calculations.

Academic Significance and Societal Importance of the Research Achievements

本研究によって，高周期14族・13族元素を配位子とする異種二核遷移金属錯体の合成法を確立し，二酸化炭素などの不活性分子変換反応におけるそれらの触媒機能を明らかにした。これらの結果は，金属錯体触媒の新しい分子設計を確立し，次世代の物質合成法開発の嚆矢となる効率的分子変換反応を実現したものであり，遷移状態制御による反応開発の有用性を実証したものとして意義深い。

Research Products

• [Journal Article] Ruthenium-catalyzed ortho C-H Borylation of Arylphosphines: A Powerful Tool for Late-Stage Modification of Phosphorus Compounds (2019)
  • 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
  • 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 Germanium (2018)
  • Author(s): J. Takaya, N. Iwasawa
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2018 Issue: 46 Pages: 5012-5018
  • DOI: 10.1002/ejic.201801257
  • Peer Reviewed
• [Journal Article] Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation (2017)
  • 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
  • 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 CO2 (2017)
  • 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
  • Peer Reviewed
• [Journal Article] Metallic Reductant-Free Synthesis of α-Substituted Propionic Acid Derivatives through Hydrocarboxylation of Alkenes with Formate Salt (2017)
  • Author(s): Takaya, J.; Miyama, K.; Zhu, C.; Iwasawa, N.
  • Journal Title: Chem. Commun. Volume: 53 Issue: 28 Pages: 3982-3985
  • DOI: 10.1039/c7cc01377a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fluorine-controlled C-H borylation of arenes catalyzed by a PSiN-pincer platinum complex (2015)
  • Author(s): Jun Takaya, Shisei Ito, Hironori Nomoto, Narumasa Saito, Naohiro Kirai and Nobuharu Iwasawa
  • Journal Title: Chemical Communications Volume: 51 Issue: 100 Pages: 17662-17665
  • DOI: 10.1039/c5cc07263h
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Use of Formate Salts as a Hydride and a CO2 Source in PGeP-Palladium Complex-Catalyzed Hydrocarboxylation of Allenes (2015)
  • Author(s): C. Zhu, J. Takaya, and N. Iwasawa
  • Journal Title: Org. Lett. Volume: 17 Issue: 7 Pages: 1814-1817
  • DOI: 10.1021/acs.orglett.5b00692
  • Peer Reviewed / Acknowledgement Compliant
• [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): Ryoske Yamada, Nobuharu Iwasawa, Jun Takaya
  • Organizer: 日本化学会第98春季年会
• [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
• [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
• [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
• [Presentation] Ru-Catalyzed C-H Borylation of Arylphosphines: A Powerful Tool for Modification of Phosphine Ligands (2018)
  • Author(s): Kazuishi Fukuda, Ryosuke Yamada, Nobuharu Iwasawa, Jun Takaya
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry
  • Int'l Joint Research
• [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Metalloligands (2018)
  • Author(s): Jun Takaya
  • Organizer: FHI-JST Joint Symposium
  • Int'l Joint Research
• [Presentation] PSiP-Platinum Complexes-Promoted C-H Bond Activation and Transformation of Benzene (2018)
  • Author(s): Ryota Nakaya, Jun Takaya, Nobuharu Iwasawa
  • Organizer: International Conference on Coordination Chemistry, 2018
  • Int'l Joint Research
• [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Group 13 Metalloligands (2018)
  • Author(s): Jun Takaya
  • Organizer: International Conference on Coordination Chemistry, 2018
  • Int'l Joint Research
• [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Group 13 Metalloligands (2018)
  • Author(s): Jun Takaya
  • Organizer: 4th International Conference on Organometallic and Catalysis 2018
  • Int'l Joint Research
• [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Metalloligands (2018)
  • Author(s): Jun Takaya
  • Organizer: The 1st Sino-Japanese Symposium on Catalysis for Precision Synthesis
  • 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
• [Presentation] Ruthenium-Catalyzed C-H Borylation of Aryl Phosphines (2018)
  • Author(s): Kazuishi Fukuda, Ryosuke Yamada, Nobuharu Iwasawa, Jun Takaya
  • Organizer: 第65回有機金属化学討論会
• [Presentation] Highly Efficient Hydrosilylation Reactions Catalyzed by Al-Pd Bimetallic Complexes (2018)
  • Author(s): Jun Takaya, Akira Shiozuka, Narumasa Saito, Nobuharu Iwasawa
  • Organizer: 第65回有機金属化学討論会
• [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Multifunctional Ligands (2018)
  • Author(s): Jun Takaya
  • Organizer: The 2nd Base Metal Catalysis Symposium ~After Discussion~
• [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
• [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
• [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
• [Presentation] 新規高周期 13 族金属-ロジウム二核錯体の合成・構造・反応性 -Al,Ga,In配位子の機能評価- (2017)
  • Author(s): 植木加奈子・斉藤成将・鷹谷 絢・岩澤伸治
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応大学（神奈川）
  • Year and Date: 2017-03-16
• [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 (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
• [Presentation] Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Al-Metalloligand in Hydrosilylation of CO2 (2017)
  • Author(s): Jun Takaya and Nobuharu Iwasawa
  • Organizer: Organometallic Chemistry Directed Toward Organic Synthesis (OMCOS19)
• [Presentation] Synthesis, Structure and Reactivity of Iridium Complexes Having a Gallium-Containing Pincer Type Ligand (2017)
  • Author(s): Narumasa Saito, Jun Takaya, Nobuharu Iwasawa
  • Organizer: Organometallic Chemistry Directed Toward Organic Synthesis (OMCOS19)
• [Presentation] 配位子の精密設計を基盤とする新しい金属触媒機能の開拓 (2017)
  • Author(s): 鷹谷 絢
  • Organizer: 日本化学会第97春季年会 特別企画「有機合成化学を起点とするものづくり戦略」
  • Place of Presentation: 慶応大学（神奈川）
  • Invited
• [Presentation] Synthesis, Structure, and Catalysis of Newly Designed Palladium Complexes Having a Heavier Group 13 Metalloligand (2017)
  • Author(s): 鷹谷 絢
  • Organizer: 日本化学会第97春季年会 「アジア国際シンポジウム」
  • Place of Presentation: 慶応大学（神奈川）
  • Int'l Joint Research / Invited
• [Presentation] Exploring New Transition Metal Catalysis Utilizing Rationally Designed Multifunctional Ligands (2016)
  • Author(s): Jun Takaya
  • Organizer: 第7回大津会議
  • Place of Presentation: 大津プリンスホテル（東京）
  • Year and Date: 2016-10-17
  • Int'l Joint Research / Invited
• [Presentation] Synthesis, Structure, and Catalysis of Newly Designed Palladium Complexes Having a Heavier Group 13 Element as a Supporting Ligand (2016)
  • Author(s): 鷹谷 絢，岩澤伸治
  • Organizer: 錯体化学会 第66回討論会
  • Place of Presentation: 福岡大学 七隈キャンパス（福岡市城南区）（福岡）
  • Year and Date: 2016-09-10
• [Presentation] ビスホスフィノターピリジンをN,P-多座配位子として利用する ガリウム-イリジウム二核金属錯体の合成と反応 (2016)
  • Author(s): 斉藤成将，鷹谷絢，岩澤伸治
  • Organizer: 錯体化学会 第66回討論会
  • Place of Presentation: 福岡大学 七隈キャンパス（福岡市城南区）（福岡）
  • Year and Date: 2016-09-10
• [Presentation] 新規PGaP-ピンサー型配位子をもつロジウム錯体の合成と反応 (2016)
  • Author(s): 植木 加奈子・斉藤 成将・鷹谷 絢・岩澤 伸治
  • Organizer: 錯体化学会 第66回討論会
  • Place of Presentation: 福岡大学 七隈キャンパス（福岡市城南区）（福岡）
  • Year and Date: 2016-09-10
• [Presentation] Synthesis, Structure, and Catalysis of New Transition Metal Complexes Having a Heavier Group 13 Element as a Supporting Ligand (2016)
  • Author(s): 鷹谷 絢
  • Organizer: the 20th International Symposium on Homogeneous Catalysis
  • Place of Presentation: 京都テルサ（京都）
  • Year and Date: 2016-07-10
  • Int'l Joint Research / Invited
• [Presentation] PSiN-ピンサー型金属錯体を触媒として用いる アレーンまたはアルケン類のホウ素化反応の開発 (2016)
  • Author(s): 伊藤 志成・鷹谷 絢・岩澤 伸治
  • Organizer: 日本化学会第96春季年会(2016)
  • Place of Presentation: 同志社大学 京田辺キャンパス（京都）
  • Year and Date: 2016-03-24
• [Presentation] Synthesis, Structure, and Reactivity of Gallium-Iridium Heterobime- tallic Complexes Utilizing an N,P-Multidentate Ligand (2016)
  • Author(s): 齋藤成将・鷹谷 絢・岩澤 伸治
  • Organizer: 日本化学会第96春季年会(2016)
  • Place of Presentation: 同志社大学 京田辺キャンパス（京都）
  • Year and Date: 2016-03-24
• [Presentation] 配位子の精密設計を基盤とする新しい金属触媒機能の開拓 (2016)
  • Author(s): 鷹谷 絢
  • Organizer: 先端物質化学講演会 ― 有機化学のフロンティア ―
  • Place of Presentation: 九州大学先導物質化学研究所（筑紫地区）（福岡）
  • Invited
• [Presentation] 新しいピンサー型錯体の創製と利用 ー触媒設計に基づく合成反応開発の面白さー (2016)
  • Author(s): 鷹谷 絢
  • Organizer: 有機元素化学セミナー
  • Place of Presentation: 中央大学（東京）
  • Invited
• [Presentation] 遷移状態制御を基盤とする多金属協同作用系触媒の理論設計 (2016)
  • Author(s): 鷹谷 絢
  • Organizer: 特設分野研究の研究代表者交流会「遷移状態制御」
  • Place of Presentation: 独立行政法人日本学術振興会（東京）
• [Presentation] 配位子の精密設計を基盤とする新しい金属触媒機能の開拓 (2016)
  • Author(s): 鷹谷 絢
  • Organizer: 分子研研究会 「若い世代が創る次世代型分子触媒の開発とその展望」
  • Place of Presentation: 分子科学研究所（岡崎）
• [Presentation] 高周期１４族元素含有ピンサー型錯体の化学 ー触媒設計に基づく合成反応開発の面白さー (2015)
  • Author(s): 鷹谷 絢
  • Organizer: パイスター分子制御による未来型物質変換研究拠点 第１回若手シンポジウム
  • Place of Presentation: 関西学院大学神戸三田キャンパス （兵庫県）
  • Year and Date: 2015-12-12
  • Invited
• [Presentation] Synthesis, Structure, and Reactivity of Gallium-Late Transition Metal Heterobimetallic Complexes (2015)
  • Author(s): 齋藤成将，鷹谷 絢，岩澤 伸治
  • Organizer: IKCOC-13
  • Place of Presentation: リーガロイヤルホテル（京都）
  • Year and Date: 2015-11-11
  • Int'l Joint Research
• [Presentation] PSiN-ピンサー型配位子をもつ白金錯体を触媒とする芳香族炭素-水素結合ホウ素化反応の開発 (2015)
  • Author(s): 伊藤 志成，野本 浩礼，斎藤 成将，喜来 直裕，鷹谷 絢，岩澤 伸治
  • Organizer: 第 62 回 有機金属化学討論会
  • Place of Presentation: 関西大学千里山キャンパス（大阪府）
  • Year and Date: 2015-09-08