Development of metal cluster catalysts by controlling the transition state for C-H bond activation on metal clusters

• Project/Area Number: 15KT0064
• 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: Osaka University
• Principal Investigator: Tsurugi Hayato 大阪大学, 基礎工学研究科, 准教授 (60432514)
• Project Period (FY): 2015-07-10 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000); Fiscal Year 2019: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2018: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2017: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2016: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2015: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: 炭素－水素結合活性化 / 金属クラスター / 金属－炭素結合 / シグマ結合メタセシス / 前周期遷移金属 / 二核錯体 / アルコキシド架橋 / ハフニウム錯体 / カチオン性錯体 / 金属クラスター錯体 / 酸素架橋 / アルコール酸化 / メタラサイクル / 構造変化 / 炭素―水素結合活性化 / イミド架橋 / クラスター錯体 / 遷移状態 / 触媒反応

Outline of Final Research Achievements

The strong interaction between more than two metals as well as the proximal effect of the metal centers have attracted recent interest for the development of new reactions specifically proceeding by the multinuclear reactive center, which has the potential to exhibit a unique reactivity beyond that of a mononuclear metal complex. In this study, the key for the reaction progress is the flexibility of the bridging ligand in dinuclear complexes, in which the carbon-hydrogen bond in the bridging ligand approaches to the metal center, and further carbon-hydrogen bond activation and functionalization was successfully observed.

Academic Significance and Societal Importance of the Research Achievements

本研究により、有機物の官能基化において重要な炭素－水素結合活性化が、従来の配向基を用いる方法ではなく、複数の金属からなる多核金属錯体を反応場とすることで配向基を用いることなく速やかに進行し、さらには単核金属錯体では成し得ない位置での反応が可能となることを見出した。多核金属錯体に特有な構造の柔軟性を用いる新たな反応開発の基盤的知見となる点で、学術的にも意義深い内容である。

Research Products

• [Journal Article] Synthesis, Structure, and Reactivity of Dicationic Bimetallic Tetrabenzyldihafnium Complexes Bearing a Chelating (2-Hydroxyethyl)amido Ligand (2020)
  • Author(s): Mariko Inoue, Michael J. Lopez, Hayato Tsurugi, Kazushi Mashima
  • Journal Title: Organometallics Volume: 39 Pages: 614-622
  • Peer Reviewed
• [Journal Article] Cβ?Cβ Bond Fission of Metallacyclopentadiene over a Low-Valent Ditantalum Scaffold (2019)
  • Author(s): Laskar Payel、Yamamoto Keishi、Nishi Kohei、Ikeda Hideaki、Tsurugi Hayato、Mashima Kazushi
  • Journal Title: Organometallics Volume: 38 Issue: 3 Pages: 722-729
  • DOI: 10.1021/acs.organomet.8b00914
  • Peer Reviewed
• [Journal Article] Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Oxo-Bridged Dinuclear Cerium Complexes with Pentadentate Schiff-Base Ligands under a Dioxygen Atmosphere (2018)
  • Author(s): Shirase Satoru、Shinohara Koichi、Tsurugi Hayato、Mashima Kazushi
  • Journal Title: ACS Catalysis Volume: 8 Issue: 8 Pages: 6939-6947
  • DOI: 10.1021/acscatal.8b01718
  • Peer Reviewed
• [Journal Article] Propargylic C(sp3)-H Bond Activation for Preparing η3-Propargyl/Allenyl Complexes of Yttrium (2017)
  • Author(s): Nagae Haruki、Kundu Abhinanda、Tsurugi Hayato、Mashima Kazushi
  • Journal Title: Organometallics Volume: 36 Issue: 16 Pages: 3061-3067
  • DOI: 10.1021/acs.organomet.7b00395
  • Peer Reviewed
• [Journal Article] Arylimido-Bridged Dinuclear Ti(μ-NAr)2Ti Scaffold for Alkyne Insertion into ortho-C-H Bond of Arylimido Ligands (2017)
  • Author(s): Haruki Nagae, Wataru Hato, Kento Kawakita, Hayato Tsurugi, Kazushi Mashima
  • Journal Title: Chemistry - A European Journal Volume: 23 Issue: 3 Pages: 586-596
  • DOI: 10.1002/chem.201603580
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Reactions of Ditantalum-Allyl Complexes Derived from Intramolecular C-H Bond Activation of the Methylene of the Ethyl Group (2016)
  • Author(s): Keishi Yamamoto, Haruki Nagae, Hayato Tsurugi, Kazushi Mashima
  • Journal Title: Organometallics Volume: 35 Issue: 14 Pages: 2384-2390
  • DOI: 10.1021/acs.organomet.6b00402
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] C(sp3)-H Alkenylation Catalyzed by Cationic Alkylhafnium Complexes: Stereoselective Synthesis of Trisubstituted Alkenes from 2,6-Dimethylpyridines and Internal Alkynes (2016)
  • Author(s): Michael J. Lopez, Ai Kondo, Haruki Nagae, Koji Yamamoto, Hayato Tsurugi, Kazushi Mashima
  • Journal Title: Organometallics Volume: 35 Issue: 22 Pages: 3816-3827
  • DOI: 10.1021/acs.organomet.6b00655
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Synthesis and Characterization of Dinuclear Bezylhafnium Complexes derived from Benzylation of (2-Hydroxyethyl)imine by Tetrabenzylhafnium (2019)
  • Author(s): Mariko Inoue, Michael J. Lopez, Hayato Tsurugi, Kazushi Mashima
  • Organizer: 錯体化学会第69回討論会
• [Presentation] ピロリルアルミネート配位子を有するチタン錯体を触媒としたアルケンのヒドロアミノアルキル化反応 (2019)
  • Author(s): 井上 まりこ、劒 隼人、真島 和志
  • Organizer: 日本化学会第99春季年会
• [Presentation] 酸素架橋マンガン三核クラスターの還元反応によるマンガン多核クラスターの合成 (2019)
  • Author(s): 鳥井 隆也、劒 隼人、真島 和志
  • Organizer: 日本化学会第99春季年会
• [Presentation] Catalytic Aerobic Oxidation of Alcohols to Carbonyl Compounds with in-situ Generated Oxo-bridged Dinuclear Cerium Complex (2018)
  • Author(s): Satoru Shirase, Koichi Shinohara, Hayato Tsurugi, Kazushi Mashima
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC14)
  • Int'l Joint Research
• [Presentation] Catalytic Oxidation of Alcohols to Aldehydes by Cerium Complexes with Pentadentate Schiff-base Ligands under O2 atmosphere (2018)
  • Author(s): Satoru Shirase, Koichi Shinohara, Yuri Ikeda, Hayato Tsurugi, Kazushi Mashima
  • Organizer: XXVIII International Conference on Organometallic Chemistry (ICOMC2018)
  • Int'l Joint Research
• [Presentation] Ortho-C-H Bond Aminoalkylation of Pyridine Derivatives Catalyzed by Yttrium Complexes with N,N’-Diarylethylenediamido Ligands (2018)
  • Author(s): Hayato Tsurugi, Mariko Inoue, Abhinanda Kundu, Haruki Nagae, Kazushi Mashima
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC14)
  • Int'l Joint Research
• [Presentation] Catalytic C(sp3)-H Bond Alkenylation of α-Methylpyridine Derivatives (2018)
  • Author(s): Hayato Tsurugi, Mariko Inoue, Michael J. Lopez, Haruki Nagae, Kazushi Mashima
  • Organizer: The 4th International Symposium on C-H Activation (ISCHA4)
  • Int'l Joint Research
• [Presentation] Transformation of Metallacyclopentadiene to Metallacyclopropeneon Bimetallic Ditantalum Scaffold (2018)
  • Author(s): Anga Srinivas、Payel Laskar、山本 啓司、劒 隼人、真島 和志
  • Organizer: 第98春季年会
• [Presentation] （2-アミド）エトキシド配位子を有するカチオン性ベンジルハフニウム二核錯体の合成 (2018)
  • Author(s): 井上 まりこ、Michael J. Lopez、劒 隼人、真島 和志
  • Organizer: 第98春季年会
• [Presentation] カチオン性アルキルハフニウム錯体を触媒としたsp3炭素?水素結合のアルケニル化による三置換アルキンの立体選択的合成 (2017)
  • Author(s): 井上 まりこ、Michael J. Lopez、劒 隼人、真島 和志
  • Organizer: 第64回有機金属化学討論会
• [Presentation] Catalytic C(sp3)-H Hydroalkylation of Internal Alkynes using 2,6-Dimethyl-N-heterocycles Catalyzed by a Cationic Alkylhafnium Complex (2016)
  • Author(s): Michael J. Lopez, Ai Kondo, Koji Yamamoto, Hayato Tsurugi, Kazushi Mashima
  • Organizer: Third International Symposium on C-H Activation
  • Place of Presentation: Montreal, Canada
  • Year and Date: 2016-05-30
  • Int'l Joint Research
• [Presentation] Ortho-C-H Bond Vinylation of Arylimido Ligands Bridging Two Titanium Centers (2016)
  • Author(s): Hayato Tsurugi, Haruki Nagae, Kazushi Mashima
  • Organizer: Third International Symposium on C-H Activation
  • Place of Presentation: Montreal, Canada
  • Year and Date: 2016-05-30
  • Int'l Joint Research
• [Remarks] 大阪大学大学院基礎工学研究科 真島研究室ホームページ
  • URL: http://www.chem.es.osaka-u.ac.jp/organomet/
• [Remarks] 真島研究室ホームページ
  • URL: http://www.chem.es.osaka-u.ac.jp/organomet/
• [Remarks] 真島研究室ＨＰ
  • URL: http://www.chem.es.osaka-u.ac.jp/organomet/
• [Remarks] 大阪大学大学院基礎工学研究科真島研Web
  • URL: http://www.organomet.chem.es.osaka-u.ac.jp/