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Synthesis and reactivity of pincer type dinuclear complexes with metal-metal dative bond

Research Project

Project/Area Number 17K05812
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionNara Women's University

Principal Investigator

Nakajima Takayuki  奈良女子大学, 自然科学系, 准教授 (80322676)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2017: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords複核錯体 / 多核錯体 / 四座ホスフィン / 協同効果 / 銅 / イリジウム / ヒドリド / ギ酸 / 水素 / 多座配位子 / Pincer / 供与結合
Outline of Final Research Achievements

We have utilized four linear tetradentate phosphine ligands with longer central methylene chains and different configurations at the inner phosphorous atoms, meso- and rac-Ph2PCH2P(Ph)(CH2)nP(Ph)CH2PPh2 (n = 2: dpmppe, 3:dpmppp, 4:dpmppb) to modulate the structures and reactivity of copper hydride species. These ligands gave a series of multinuclear copper hydride complexes with a variety of metal frameworks. Among these copper hydride complexes, only the copper hydride supported by meso-dpmppb showed reactivity toward CO2. Furthermore, the copper hydride was found to be a suitable catalyst for formic acid dehydrogenation into H2 and CO2. An unsymmetric dinuclear copper motif bridged by tetradentate phosphine ligands, was proposed as an active species to promote the decomposition of FA by virtue of synergistic effects of the Cu2 unit. The present system is the first distinguished catalytic dehydrogenation of FA by using cheap base metallic Cu complexes.

Academic Significance and Societal Importance of the Research Achievements

貴金属に代わり安価な卑金属を用いて同等の活性を持つ触媒反応の開発は元素戦略の観点から重要である。今回,四座ホスフィン配位子に安定に支持された銅2核中心が協同的に作業することで今までにない優れた触媒活性をもつギ酸の分解反応を見出したことは,今度の触媒反応開発に置いて重要な指針を与えるものである。また,これまで他のホスフィン配位子に比べ利用例が少ない四座ホスフィン配位子の有用性を実験的にも明らかにできたことは多座ホスフィン配位子の設計や合成,それを用いた錯体合成ならびに反応性など,錯体化学,有機金属化学,触媒化学の多方面に大きな影響を与える結果だと考えられる。

Report

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

    (41 results)

All 2020 2019 2018 2017 Other

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Open Access: 1 results) Presentation (28 results) (of which Int'l Joint Research: 3 results,  Invited: 1 results) Remarks (1 results)

  • [Journal Article] Facially Dispersed Polyhydride Cu9 and Cu16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks2020

    • Author(s)
      Nakamae Kanako、Nakajima Takayuki、Ura Yasuyuki、Kitagawa Yasutaka、Tanase Tomoaki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 6 Pages: 2262-2267

    • DOI

      10.1002/anie.201913533

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Transition Metal Clusters Constrained by Linear Tetradentate Phosphine Ligands2020

    • Author(s)
      Nakajima Takayuki、Tanase Tomoaki
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 4 Pages: 386-394

    • DOI

      10.1246/cl.200041

    • NAID

      130007828858

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh22019

    • Author(s)
      Tanase Tomoaki、Otaki Risa、Okue Ayumi、Nakamae Kanako、Nakajima Takayuki
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2019 Issue: 37 Pages: 3993-4005

    • DOI

      10.1002/ejic.201900785

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Tetra-, hexa- and octanuclear copper hydride complexes supported by tridentate phosphine ligands2019

    • Author(s)
      Nakajima Takayuki、Nakamae Kanako、Hatano Rika、Imai Kaho、Harada Masafumi、Ura Yasuyuki、Tanase Tomoaki
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 32 Pages: 12050-12059

    • DOI

      10.1039/c9dt02467k

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synergistic Cu2 Catalysts for Formic Acid Dehydrogenation2019

    • Author(s)
      Nakajima Takayuki、Kamiryo Yoshia、Kishimoto Masayo、Imai Kaho、Nakamae Kanako、Ura Yasuyuki、Tanase Tomoaki
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 22 Pages: 8732-8736

    • DOI

      10.1021/jacs.9b03532

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Alloyed Tetranuclear Metal Chains of Pd4-nPtn (n = 0-3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge2019

    • Author(s)
      Tanase Tomoaki、Tanaka Miho、Hamada Mami、Morita Yuka、Nakamae Kanako、Ura Yasuyuki、Nakajima Takayuki
    • Journal Title

      Chemistry A European Journal

      Volume: 25 Issue: 35 Pages: 8219-8224

    • DOI

      10.1002/chem.201901701

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] N-Acyclic carbene complexes supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an asymmetric pincer ligand2019

    • Author(s)
      Tanase Tomoaki、Urabe Mari、Mori Natsumi、Hatada Satoko、Noda Sayo、Takenaka Hiroe、Nakamae Kanako、Nakajima Takayuki
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 879 Pages: 47-59

    • DOI

      10.1016/j.jorganchem.2018.10.005

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] A decanuclear Pt complex comprised of an unbridged Pt4 chain capped by two Pt3 A-frame units supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh22019

    • Author(s)
      Tanase Tomoaki、Urabe Mari、Takenaka Hiroe、Nakamae Kanako、Nakajima Takayuki
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 883 Pages: 41-46

    • DOI

      10.1016/j.jorganchem.2019.01.010

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and characterization of iridium hydride complexes with meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an unsymmetric pincer ligand2019

    • Author(s)
      Tanase Tomoaki、Mori Natsumi、Nakamae Kanako、Nakajima Takayuki
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 888 Pages: 54-64

    • DOI

      10.1016/j.jorganchem.2019.03.010

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands2018

    • Author(s)
      Nakajima Takayuki、Kamiryo Yoshia、Hachiken Kanae、Nakamae Kanako、Ura Yasuyuki、Tanase Tomoaki
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 17 Pages: 11005-11018

    • DOI

      10.1021/acs.inorgchem.8b01628

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Reactivity of Thiolate-Bridged NiIIMI Heterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2 Metalloligand2017

    • Author(s)
      Kure Bunsho、Sano Mikie、Watanabe Natsuki、Nakajima Takayuki、Tanase Tomoaki
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2017 Issue: 35 Pages: 4097-4109

    • DOI

      10.1002/ejic.201700682

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Fluxinal Cu8H6 Cluster Supported by Bis(diphenyphosphino)methane and Its Facile Reaction with CO22017

    • Author(s)
      Nakamae, Kanako; Tanaka, Miho; Kure, Bunsho; Nakajima, Takayuki; Ura, Yasuyuki; Tanase, Tomoaki*
    • Journal Title

      Chemistry- A European Journal

      Volume: 印刷中 Issue: 40 Pages: 9457-9461

    • DOI

      10.1002/chem.201702071

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] 四座ホスフィン配位子に支持された非対称Ir二核錯体の合成と反応性2020

    • Author(s)
      前田侑希,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      日本化学会第100回春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 四座ホスフィン配位子に支持されたPd/Pt 混合金属四核錯体の合成2020

    • Author(s)
      森田優花,藤澤良実,中前佳那子,中島隆行, 棚瀬知明
    • Organizer
      日本化学会第100回春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 四座ホスフィン配位子に支持されたMCu異種金属二核錯体 (M = Ni, Pd, Pt) の合成と反応2020

    • Author(s)
      田窪瑞季,今井香歩,中前佳那子,中島隆行, 棚瀬知明
    • Organizer
      日本化学会第100回春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 非対称銅二核錯体触媒を用いたギ酸の分解反応機構2019

    • Author(s)
      今井香歩, 中前佳那子, 浦康之, 中島隆行, 棚瀬知明
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] アミノ基を有する四座ホスフィンに支持されたRh二核錯体の合成と反応性2019

    • Author(s)
      前田侑希,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      第69回錯体化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] PNP架橋を有する新奇直鎖状四座ホスフィンに支持されたPd/Pt混合金属4核鎖の合成と反応2019

    • Author(s)
      森田優花, 田中美帆, 濱田磨美, 中前佳那子, 浦康之, 中島隆行, 棚瀬知明
    • Organizer
      第69回錯体化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Linear Mixed-Metal Pd4-nPtn (n = 0-3) Tetranuclear Complexes Supported by Imino-bridged Tetraphosphines, rac-dpmppan2019

    • Author(s)
      Miho Tanaka, Kanako Nakamae, Yasuyuki Ura, Takayuki Nakajima, Tomoaki Tanase
    • Organizer
      日本化学会第99回春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Chiral Octapalladium Chains2019

    • Author(s)
      Kanako Nakamae, Takayuki Nakajima, Tomoaki Tanase
    • Organizer
      日本化学会第99回春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] アミノ基を有する新奇四座ホスフィン配位子に支持されたRh二核錯体の合成とHClとの反応性2019

    • Author(s)
      前田侑希、中前佳那子、中島隆行、棚瀬知明
    • Organizer
      日本化学会第99回春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Hydrogenation of CO2 Catalyzed by Dinuclear Copper Hydride Complexes2019

    • Author(s)
      Kanako Nakamae, Takayuki Nakajima, Tomoaki Tanase
    • Organizer
      The 99th CSJ Annual Meeting
    • Related Report
      2018 Research-status Report
  • [Presentation] Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands2018

    • Author(s)
      Takayuki Nakajima, Yoshia Kamiryo, Kanae Hachiken, Kanako Nakamae, Yasuyuki Ura, Tomoaki Tanase
    • Organizer
      The 43st International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and Its Facile Reaction with CO22018

    • Author(s)
      Miho Tanaka, Kanako Nakamae, Yasuyuki Ura, Bunsho Kure, Takayuki Nakajima, and Tomoaki Tanase
    • Organizer
      The 43st International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] 四座ホスフィンmeso-dpmppmで支持したイリジウム(I)単核錯体の合成と反応性2018

    • Author(s)
      森菜摘,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 多座ホスフィン配位子を用いた銅ヒドリド多核錯体の合成2018

    • Author(s)
      秦野莉佳,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 直鎖状四座ホスフィン配位子に支持された銅(I)ヒドリド多核錯体の合成及び構造2018

    • Author(s)
      岸本雅世,上領美彩,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] アミノ基を有する新奇直鎖状四座ホスフィンに支持された遷移金属多核錯体2018

    • Author(s)
      田中美帆,濱田磨美,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 四座ホスフィンmeso-dpmppmを用いた白金多核錯体の合成と反応性2018

    • Author(s)
      卜部万里,中前佳那子,中島隆行,棚瀬知明
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Synthesis and Reactivity of Dinuclear Complexes Supported by Tetradentate Phosphine Ligands2017

    • Author(s)
      Takayuki NAKAJIMA,* Kanako NAKAMAE, Bunsho KURE, and Tomoaki TANASE
    • Organizer
      International Symposium on Pure & Applied Chemistry 2017 (ISPAC2017)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Pd4核ユニット間の不斉自己認識によるホモキラルな四座ホスフィンに支持された直鎖状Pd8核錯体の生成2017

    • Author(s)
      金子由妃乃・山本佳奈・森田惟美・中前佳那子・久禮文章・中島隆行・棚瀬知明
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 四座ホスフィンに支持された銅(I)二核及び四核イソシアニド錯体の合成と構造及び平衡反応2017

    • Author(s)
      上領美彩、八軒可奈恵、中前佳那子、久禮文章、中島隆行、棚瀬知明
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 分岐型ホスフィン配位子に支持された銅(I)及び金(I)多核錯体の合成と性質2017

    • Author(s)
      小池香菜子・中前佳那子・久禮文章・中島隆行・棚瀬知明
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 四座ホスフィン配位子とジイミン系配位子に支持された銅(I)二核錯体の合成と発光特性2017

    • Author(s)
      三木田ゆみな・中前佳那子・久禮文章・中島隆行・棚瀬知明
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 四座ホスフィンmeso-dpmppmを用いたピンサー型白金単核錯体の合成と反応性2017

    • Author(s)
      卜部万里・森菜摘・中前佳那子・久禮文章・中島隆行・棚瀬知明
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 銅 8 核ヒドリド錯体を用いた二酸化炭素のヒドロシリル化を 伴うジシロキサン生成反応2017

    • Author(s)
      田中美帆・・中前佳那子・浦康之・久禮文章・中島隆行・棚瀬知明
    • Organizer
      第67回錯体化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and Its Facile Reaction with CO22017

    • Author(s)
      Miho Tanaka, Kanako Nakamae, Yasuyuki Ura, Bunsho Kure, Takayuki Nakajima, and Tomoaki Tanase
    • Organizer
      4th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry
    • Related Report
      2017 Research-status Report
  • [Presentation] アミノ基を有する新奇直鎖状四座ホスフィン rac-dpmppan に支持されたパラジウム4核錯体の合成2017

    • Author(s)
      田中美帆、中前佳那子、久禮文章、中島隆行、棚瀬知明
    • Organizer
      日本化学会第98回春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 直鎖状四座ホスフィンmeso-dpmppmに支持されたAフレーム型白金3核錯体の合成と反応2017

    • Author(s)
      卜部万里・中前佳那子・久禮文章・中島隆行・棚瀬知明
    • Organizer
      日本化学会第98回春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 四座ホスフィン配位子meso-dpmpppで支持されたロジウム二核錯体のアミン類による還元的脱塩素化反応2017

    • Author(s)
      西垣真利子・松井彩・中前佳那子・久禮文章・中島隆行・棚瀬知明
    • Organizer
      日本化学会第98回春季年会
    • Related Report
      2017 Research-status Report
  • [Remarks] Tanase Group Home Page

    • URL

      http://www.chem.nara-wu.ac.jp/~tanase/TanaseGroup/

    • Related Report
      2017 Research-status Report

URL: 

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

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