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Synthesis and Applications of Noninnocent Phosphaalkene Ligands

Research Project

Project/Area Number 26288050
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

Ozawa Fumiyuki  京都大学, 化学研究所, 教授 (40134837)

Co-Investigator(Renkei-kenkyūsha) TAKEUCHI Katsuhiko  京都大学, 化学研究所, 助教 (90724097)
Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥16,770,000 (Direct Cost: ¥12,900,000、Indirect Cost: ¥3,870,000)
Fiscal Year 2016: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2015: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2014: ¥9,230,000 (Direct Cost: ¥7,100,000、Indirect Cost: ¥2,130,000)
Keywordsホスファアルケン / ノンイノセント配位子 / ピンサー錯体 / 合成化学 / 遷移金属錯体 / ホスファアルケン配位子
Outline of Final Research Achievements

It has been documented that pyridine-based PNP-pincer ligands coordinated with transition metals undergo deprotonation at the benzylic position. The resulting ligands having a dearomatized pyridine unit act as a strong base, to cause metal-ligand cooperative activation of chemical bonds in a heterolytic manner. In this study, we attempted to improve the reactivity by introducing a phosphaalkene unit possessing strong π-accepting properties toward transition metals into the ligand framework. We succeeded in the synthesis of PNP-pincer type phosphaalkene complexes, which exhibit extremely high reactivity toward N-H bond cleavage of ammonia and catalytic hydrosilylation of carbon dioxide.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Annual Research Report
  • 2014 Annual Research Report

Research Products

(25 results)

All 2017 2016 2015 2014 Other

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 5 results) Presentation (18 results) (of which Int'l Joint Research: 4 results,  Invited: 2 results) Remarks (2 results)

  • [Journal Article] PNP-Pincer Type Phosphaalkene Complexes of Late Transition Metals2016

    • Author(s)
      Fumiyuki Ozawa and Yumiko Nakajima
    • Journal Title

      Chem. Rec.

      Volume: 16 Pages: 2314-2323

    • DOI

      10.1002/tcr.201600054

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Unsymmetircal PNP-Pincer Type Phosphaalkene Ligands Protected by a Fused- Ring Bulky Eind Group: Synthesis and Applications to Rh(I) and Ir(I) Complexes2016

    • Author(s)
      H. Taguchi, D. Sasaki, K. Takeuchi, S. Tsujimoto, T. Matsuo, H. Tanaka, K. Yoshizawa, F. Ozawa
    • Journal Title

      Organometallics

      Volume: 35 Pages: 1526-1533

    • DOI

      10.1021/acs.organomet.6b00113

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Iridium(I) Complexes Bearing a Noninnocent PNP-Pincer Type Phosphaalkene Ligand: Catalytic Application to Base-Free N-Alkylation of Amines with Alcohols2016

    • Author(s)
      Yung-Hung Chang, Ippei Tanigawa, Hiro-omi Taguchi, Katsuhiko Takeuchi, and Fumiyuki Ozawa
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2016 Pages: 754-760

    • DOI

      10.1002/ejic.201500900

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] C-H Bond Cleavage of Acetonitrile by Iridium Complexes Bearing PNP-Pincer Type Phosphaalkene Ligands2015

    • Author(s)
      Yung-Hung Chang, Katsuhiko Takeuchi, Masayuki Wakioka, and Fumiyuki Ozawa
    • Journal Title

      Organometallics

      Volume: 34 Pages: 1957-1962

    • DOI

      10.1021/acs.organomet.5b00207

    • Related Report
      2015 Annual Research Report 2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Catalytic Synthesis of an Unsymmetrical PNP-Pincer Type Phosphaalkene Ligand2015

    • Author(s)
      Hiro-omi Taguchi, Yung-Hung Chang, Katsuhiko Takeuchi, and Fumiyuki Ozawa
    • Journal Title

      Organometallics

      Volume: 34 Pages: 1589-1596

    • DOI

      10.1021/acs.organomet.5b00195

    • Related Report
      2015 Annual Research Report 2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] PNPピンサー型ホスファアルケン配位子を有するT字形カチオン性銅錯体の合成とCO2還元触媒への応用2017

    • Author(s)
      田中裕人・竹内勝彦・小澤文幸
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] Synthesis of Ir(I) and Rh(I) complexes bearing a noninnocent PNP-pincer type phosphaalkene ligand (Eind-PPEP) and their application for catalytic hydrosilylation of CO22016

    • Author(s)
      Hiro-omi Taguchi, Katsuhiko Takeuchi, Daichi Sasaki, Shota Tsujimoto, Tsukasa Matsuo and Fumiyuki Ozawa
    • Organizer
      20th International Symposium on Homogeneous Catalysis (ISHC20)
    • Place of Presentation
      京都テレサ
    • Year and Date
      2016-07-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ノンイノセントPNPピンサー型ホスファアルケンイリジウム(I)錯体によるCO2の触媒的ヒドロシリル化反応2016

    • Author(s)
      田口廣臣・竹内勝彦・田中宏昌・吉澤一成・小澤文幸
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザホテル神戸
    • Year and Date
      2016-06-02
    • Related Report
      2016 Annual Research Report
  • [Presentation] 新規PNPピンサー型ホスファアルケン配位子Eind2-BPEPの合成と10族金属錯体への適用2016

    • Author(s)
      谷川一平・田口廣臣・竹内勝彦・辻本祥太・松尾 司・小澤文幸
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] ノンイノセントPNPピンサー型ホスファアルケン配位子Eind-PPEPの合成と鉄および銅錯体への適用2016

    • Author(s)
      佐々木大智・田中裕人・田口廣臣・竹内勝彦・辻本祥太・松尾 司・小澤文幸
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Non-innocent PNP-pincer type phosphaalkene ligands: A powerful tool for metal-ligand cooperative activation of inert molecules2015

    • Author(s)
      Fumiyuki Ozawa
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Catalytic hydrosilylation of CO2 using an iridium(I) complex bearing unsymmetrical PNP-pincer type phosphaalkene ligands2015

    • Author(s)
      Yung-Hung Chang, Katsuhiko Takeuchi and Fumiyuki Ozawa
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Unsymmetrical PNP-pincer type phosphaalkene ligands with Rind groups: Synthesis and application to rhodium(I) and iridium(I) complexes2015

    • Author(s)
      Hiro-omi Taguchi, Daichi Sasaki, Yung-Hung Chang, Katsuhiko Takeuchi, Shota Tsujimoto, Tsukasa Matsuo and Fumiyuki Ozawa
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ノンイノセント PNP ピンサー型ホスファアルケン配位子 Rind-PPEPの合成と触媒反応への応用2015

    • Author(s)
      佐々木大智・田口廣臣・竹内勝彦・辻本祥太・松尾 司・小澤文幸
    • Organizer
      第116回触媒討論会
    • Place of Presentation
      三重大学 津キャンパス
    • Year and Date
      2015-09-16
    • Related Report
      2015 Annual Research Report
  • [Presentation] ノンイノセント PNP ピンサー型ホスファアルケン配位子 Rind-PPEP を有する遷移金属錯体の合成、構造および反応性2015

    • Author(s)
      田口廣臣・佐々木大智 ・竹内勝彦・辻本祥太・松尾 司・小澤文幸
    • 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
    • Year and Date
      2015-09-07
    • Related Report
      2015 Annual Research Report
  • [Presentation] Rind基を有する非対称PNPピンサー型ホスファアルケン配位子の合成とロジウムおよびイリジウム錯体への適用2015

    • Author(s)
      田口廣臣, 佐々木大智, 張 永宏, 竹内勝彦, 辻本祥太, 松尾 司, 小澤文幸
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学船橋キャンパス
    • Year and Date
      2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] Synthesis and Reactions of PNP-Pincer Type Phosphaalkene Complexes of Iridium(I): A Remarkable Enhancement of Reactivity by a P=C Double Bond2014

    • Author(s)
      Fumiyuki Ozawa
    • Organizer
      The 16th Korea-Japan Joint Symposium on Organometallic and Coordination Chemistry
    • Place of Presentation
      東北大学片平キャンパス
    • Year and Date
      2014-10-24
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] PNPピンサー型ホスファアルケンイリジウム錯体を用いる二酸化炭素の触媒的ヒドロシリル化反応2014

    • Author(s)
      張 永宏, 竹内勝彦, 小澤文幸
    • Organizer
      第18回ケイ素化学協会シンポジウム
    • Place of Presentation
      ラフォーレ那須
    • Year and Date
      2014-10-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] ピンサー型ホスファアルケンイリジウム錯体を用いる二酸化炭素の触媒的ヒドロシリル化反応2014

    • Author(s)
      張 永宏, 竹内勝彦, 小澤文幸
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九州大学病院キャンパス
    • Year and Date
      2014-09-23
    • Related Report
      2014 Annual Research Report
  • [Presentation] 非対称性PNPピンサー型ホスファアルケン配位子を含む遷移金属錯体の合成と反応2014

    • Author(s)
      田口廣臣, 張 永宏, 竹内勝彦, 小澤文幸
    • Organizer
      第64回錯体化学討論会
    • Place of Presentation
      中央大学後楽園キャンパス
    • Year and Date
      2014-09-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] C-H Bond Cleavage of Acetonitrile by Iridium Complexes Bearing a Noninnocent PNP-Pincer Type Phosphaalkene Ligand2014

    • Author(s)
      Yung-Hung Chang and Fumiyuki Ozawa
    • Organizer
      The 26th International Conference on Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌
    • Year and Date
      2014-07-16
    • Related Report
      2014 Annual Research Report
  • [Presentation] Catalytic Synthesis of an Unsymmetrical PNP-Pincer Type Phosphaalkene Ligand2014

    • Author(s)
      Hiro-omi Taguchi, Katsuhiro Takeuchi, and Fumiyuki Ozawa
    • Organizer
      The 26th International Conference on Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌
    • Year and Date
      2014-07-16
    • Related Report
      2014 Annual Research Report
  • [Presentation] PNP-Pincer Type Phosphaalkene Complexes of Iridium: A Remarkable Enhancement of Reactivity by a P=C Double Bond2014

    • Author(s)
      Fumiyuki Ozawa, Yung-Hung Chang, Yumiko Nakajima, Hiromasa Tanaka, and Kazunari Yoshizawa
    • Organizer
      The 26th International Conference on Organometallic Chemistry
    • Place of Presentation
      ロイトン札幌
    • Year and Date
      2014-07-15
    • Related Report
      2014 Annual Research Report
  • [Remarks] 京都大学化学研究所・小澤研究室

    • URL

      http://om.kuir.kyoto-u.ac.jp

    • Related Report
      2016 Annual Research Report
  • [Remarks] 京都大学化学研究所・小澤研究室

    • URL

      http://om.kuicr.kyoto-u.ac.jp

    • Related Report
      2015 Annual Research Report 2014 Annual Research Report

URL: 

Published: 2014-04-04   Modified: 2018-03-22  

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