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Synthesis and Properties of Chalcogenocarbonyl Complexes with a Half-Sandwiched Structure

Research Project

Project/Area Number 17K05817
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionTokyo University of Science

Principal Investigator

Mutoh Yuichiro  東京理科大学, 理学部第一部化学科, 講師 (50453676)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywordsルテニウム / セレン / テルル / ハーフサンドイッチ / セレノカルボニル / テルロカルボニル / シクロペンタジエニル / 金属錯体 / 有機金属化学 / 立体化学 / イソシアニド
Outline of Final Research Achievements

The first half-sandwich type ruthenium tellurocarobnyl (CTe) complex was synthesized by the ligand substitution reaction of our CTe complex with cyclopentadienyl anion (Cp) in the presence of triethylborane. This method enabled the synthesis of a complete series of chalcogenocarbonyl (CE; E = O, S, Se, Te) complexes. The obtained CpCE compounds were characterized by NMR spectroscopy and X-ray crystallography, and the π-accepting ability of the CE ligands increases upon descending Group 16 from oxygen to tellurium. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.

Academic Significance and Societal Importance of the Research Achievements

合成不可能だった有機金属錯体に対して、自身の研究成果をもとにした独自のアプローチをにより、一連のハーフサンドイッチ型ルテニウムのカルコゲノカルボニル (CE) 錯体の合成法の開発に成功した。異なる配位構造をもつ金属錯体でも、カルコゲン原子Eが高周期になるにつれてCE配位子のπ受容性が強くなる特性が明らかとなり、本研究の学術的新規性は高い。得られた金属錯体はルテニウムが立体中心であり、金属中心性不斉錯体としての活用が期待される。このように本研究は、これまで希少であったテルロカルボニル配位子をもつ金属化合物を含めて、カルコゲノカルボニル錯体の化学に対するより良い理解に貢献するものである。

Report

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

    (25 results)

All 2020 2019 2018 2017

All Journal Article (17 results) (of which Peer Reviewed: 17 results,  Open Access: 4 results) Presentation (8 results) (of which Int'l Joint Research: 4 results,  Invited: 1 results)

  • [Journal Article] Synthesis of lactone-fused pyrroles by ruthenium-catalyzed 1,2-carbon migration-cycloisomerization2020

    • Author(s)
      Takuma Watanabe, Yuichiro Mutoh, Shinichi Saito
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 18 Issue: 1 Pages: 81-85

    • DOI

      10.1039/c9ob02363a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of Helical 3,3′-Bridged-2,2′-bibenzo[g]quinolines2020

    • Author(s)
      Yamazaki Yukari、Mizuma Risa、Abe Haruka、Aoki Rino、Mutoh Yuichiro、Saito Shinichi
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 2 Pages: 133-136

    • DOI

      10.1246/cl.190803

    • NAID

      130007795155

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and properties of anionic ruthenium thionitrosyl and selenonitrosyl complexes that contain tetraanionic 2-hydroxybenzamidobenzene ligands2020

    • Author(s)
      Fung Chi-Wai、Fukada Go、Mutoh Yuichiro、Tsuchida Noriko、Saito Shinichi
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 3 Pages: 613-624

    • DOI

      10.1039/c9dt04219a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis and Systematic Structural Analysis of Cationic Half‐Sandwich Ruthenium Chalcogenocarbonyl Complexes2020

    • Author(s)
      Suzuki Ayumi、Mutoh Yuichiro、Tsuchida Noriko、Fung Chi‐Wai、Kikkawa Shoko、Azumaya Isao、Saito Shinichi
    • Journal Title

      Chemistry ? A European Journal

      Volume: 26 Issue: 17 Pages: 3795-3802

    • DOI

      10.1002/chem.201904600

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Dimensional Single-Helix Coordination Polymer Self-assembled by Crown-Ether Appended-N-Heteroacene Radical Anion2019

    • Author(s)
      Kyosuke Isoda,* Hinako Takahashi, Yuichiro Mutoh, Norihisa Hoshino, Tomoyuki Akutagawa
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 35 Pages: 13125-13129

    • DOI

      10.1039/c9dt02797a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed (Z)-Selective Hydroboration of Terminal Alkynes with Naphthalene-1,8-diaminatoborane2019

    • Author(s)
      Yamamoto Kensuke、Mohara Yusei、Mutoh Yuichiro、Saito Shinichi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 43 Pages: 17042-17047

    • DOI

      10.1021/jacs.9b06910

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reversibly/irreversibly stimuli-responsive inks based on N-heteroacene liquids2019

    • Author(s)
      Isoda Kyosuke、Matsubara Miwa、Ikenaga Ayumi、Akiyama Yuichi、Mutoh Yuichiro
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 7 Issue: 45 Pages: 14075-14079

    • DOI

      10.1039/c9tc05195c

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Suzuki?Miyaura Cross-Coupling of 1,8-Diaminonaphthalene (dan)-Protected Arylboronic Acids2019

    • Author(s)
      Mutoh Yuichiro、Yamamoto Kensuke、Saito Shinichi
    • Journal Title

      ACS Catalysis

      Volume: 10 Issue: 1 Pages: 352-357

    • DOI

      10.1021/acscatal.9b03667

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stimuli-Responsive Room-Temperature N-Heteroacene Liquid: In Situ Observation of the Self-Assembling Process and Its Multiple Properties2019

    • Author(s)
      Isoda Kyosuke、Ishiyama Tatsuya、Mutoh Yuichiro、Matsukuma Daisuke
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 11 Issue: 12 Pages: 12053-12062

    • DOI

      10.1021/acsami.8b21695

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Evaluation of the Steric Bulk of Substituents Utilizing the Shuttling Behavior of [2]Rotaxanes with N-Arylpyrrole Moieties2018

    • Author(s)
      Yamashita Yoshiaki、Saito Yuuki、Kikkawa Shoko、Mutoh Yuichiro、Hosoya Shoichi、Azumaya Isao、Saito Shinichi
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2019 Issue: 21 Pages: 3412-3420

    • DOI

      10.1002/ejoc.201801476

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Tuning the Electronic Properties and Acid-Response Behavior of N-Heteroacene-Based π-Conjugated Liquids by Changing the Number of π-Conjugated Substituents2018

    • Author(s)
      Sato Yuika、Mutoh Yuichiro、Matsukuma Daisuke、Nakagawa Makoto、Kawai Takeshi、Isoda Kyosuke
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 13 Issue: 18 Pages: 2619-2625

    • DOI

      10.1002/asia.201800631

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed Cycloisomerization of 2-Alkynylstyrenes via 1,2-Carbon Migration That Leads to Substituted Naphthalenes2018

    • Author(s)
      Watanabe Takuma、Abe Haruka、Mutoh Yuichiro、Saito Shinichi
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 45 Pages: 11545-11549

    • DOI

      10.1002/chem.201802413

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] A ruthenium tellurocarbonyl (CTe) complex with a cyclopentadienyl ligand: systematic studies of a series of chalcogenocarbonyl complexes [CpRuCl(CE)(H2IMes)] (E = O, S, Se, Te)2017

    • Author(s)
      Suzuki Ayumi、Arai Takahiro、Ikenaga Kota、Mutoh Yuichiro、Tsuchida Noriko、Saito Shinichi、Ishii Youichi
    • Journal Title

      Dalton Transactions

      Volume: 46 Issue: 1 Pages: 44-48

    • DOI

      10.1039/c6dt04440a

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed Cycloisomerization of 2-Alkynylanilides: Synthesis of 3-Substituted Indoles by 1,2-Carbon Migration2017

    • Author(s)
      Watanabe Takuma、Mutoh Yuichiro、Saito Shinichi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 23 Pages: 7749-7752

    • DOI

      10.1021/jacs.7b04564

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of [2]Catenanes by Intramolecular Sonogashira-Type Reaction2017

    • Author(s)
      Ito Ken、Mutoh Yuichiro、Saito Shinichi
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 82 Issue: 12 Pages: 6118-6124

    • DOI

      10.1021/acs.joc.7b00672

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Tricyclic Benzazocines by Aza-Prins Reaction2017

    • Author(s)
      Katamura Tomohiro、Shimizu Tomoaki、Mutoh Yuichiro、Saito Shinichi
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 1 Pages: 266-269

    • DOI

      10.1021/acs.orglett.6b03577

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] (Z)-Selective Hydrosilylation of Terminal Alkynes with HSiMe(OSiMe3)2 Catalyzed by a Ruthenium Complex Containing an N-Heterocyclic Carbene2017

    • Author(s)
      Mutoh Yuichiro、Mohara Yusei、Saito Shinichi
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 19 Pages: 5204-5207

    • DOI

      10.1021/acs.orglett.7b02477

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] Synthesis and Properties of Cationic Ruthenium Chalcogenocarbonyl Complexes with a Half-sandwich Structure2019

    • Author(s)
      Yuichiro Mutoh, Ayumi Suzuki, Noriko Tsuchida, Shinichi Saito
    • Organizer
      14th International Conference on the Chemistry of Selenium and Tellurium (ICCST-14)
    • Related Report
      2019 Annual Research Report 2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Structure of Anionic Ruthenium Chalcogenonitrosyl Complexes with Amidato-Phenolato Ligands2019

    • Author(s)
      Chi-Wai Fung, Yuichiro Mutoh, and Shinichi Saito
    • Organizer
      14th International Conference on the Chemistry of Selenium and Tellurium (ICCST-14)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Properties of Anionic Ruthenium Complexes with a Selenonitrosyl Ligand2019

    • Author(s)
      FUNG, Chi-Wai; FUKADA, Go; TSUCHIDA, Noriko; MUTOH, Yuichiro; SAITO, Shinichi
    • Organizer
      日本化学会第99春季年会(2019)
    • Related Report
      2019 Annual Research Report
  • [Presentation] Anionic Ruthenium Thio- and Selenonitrosyl Complexes with a Tetraanionic Amidato-Phenolato Ligand (PA-22)2018

    • Author(s)
      Chi-Wai Fung, Go Fukada, Yuichiro Mutoh, Shinichi Saito
    • Organizer
      28th International Symposium on the Organic Chemistry of Sulfur (ISOCS-28)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Ruthenium-Catalyzed Cycloisomerization of 2-Alkynylanilides Leading to 3-Substituted Indoles via 1,2-Carbon Migration2018

    • Author(s)
      Yuichiro Mutoh
    • Organizer
      NTERNATIONAL CONGRESS ON PURE & APPLIED CHEMISTRY (ICPAC) 2018
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Ru上に不斉点を持つカルコゲノカルボニル錯体の合成とそれらの立体化学に及ぼす配位子の影響2017

    • Author(s)
      鈴木 あゆみ、武藤 雄一郎、斎藤 慎一
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] ルテニウム触媒存在下における炭素置換基の転位を伴う2-アルキニルアニリドの環化異性化反応の開発:3-置換インドール誘導体の合成2017

    • Author(s)
      渡辺 拓真、武藤 雄一郎、斎藤 慎一
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 炭素置換基の転位を伴う3-置換インドール誘導体の合成2017

    • Author(s)
      渡辺 拓真、武藤 雄一郎、斎藤 慎一
    • Organizer
      第7回CSJ化学フェスタ
    • Related Report
      2017 Research-status Report

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Published: 2017-04-28   Modified: 2021-02-19  

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