Control of transition state based on addition and elimination of M-M bonds

• Project/Area Number: 17KT0102
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 特設分野
• Research Field: Transition State Control
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Yamamoto Koji 東京工業大学, 物質理工学院, 助教 (70647198)
• Project Period (FY): 2017-07-18 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: 遷移状態制御 / M-M結合 / E-Z異性化 / E-Z異性化反応 / 錯体化学 / ジエン

Outline of Final Research Achievements

Olefin isomerization is useful in controlling the E/Z configuration of olefinic substrates. In thermal reaction conditions, thermodynamically more stable E-olefins are usually formed. Herein, we developed the thermal E to Z isomerization of 1,3-diene using dicationic Pd(I)-Pd(I) dinuclear complexes.

Academic Significance and Societal Importance of the Research Achievements

アルケン類のE-Z異性化反応は可逆的な反応であり、一般的には熱力学的なE体アルケンが優先的に得られる。熱力学的にE体からZ体へ異性化させることは困難であり、この反応を達成する為には光反応が用いられている。一方で、光励起を必要としない、熱反応による異性化はほとんど例がない。そのような背景のもと、Pd(I)-Pd(I)二核錯体を用いることで、選択的なE体からZ体への異性化反応を見出した。本成果は、錯体化学や有機金属化学、合成化学など幅広い分野にわたって重要な知見となることが期待できる。

Research Products

• [Journal Article] Photo-induced Translocation of a Pdn Moiety (n = 2, 7) on a Conjugated Polyene Ligand (2019)
  • Author(s): Yamashita, M.; Horiuchi, S.; Yamamoto, K.; Murahashi, T.
  • Journal Title: Dalton Trans. Volume: 48 Issue: 35 Pages: 13149-13153
  • DOI: 10.1039/c9dt03073e
  • Peer Reviewed
• [Journal Article] Exceeding Metal Capacity in Sandwich Complexes: Ligand-unsupported Docking of Extra Metal Moieties at Edges of a Metal Sheet Sandwich Complex (2019)
  • Author(s): Ishikawa, T.; Kawamura, A.; Sugawa, T.; Moridaira, R.;Yamamoto, K.; Murahashi, T.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 58 Issue: 43 Pages: 15318-15323
  • DOI: 10.1002/anie.201908850
  • Peer Reviewed
• [Journal Article] Extended Open‐Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters (2018)
  • Author(s): Yamashita Mitsuki、Kawasumi Yuna、Tachibana Yuki、Horiuchi Shinnosuke、Yamamoto Koji、Murahashi Tetsuro
  • Journal Title: Chemistry ー A European Journal Volume: 25 Issue: 5 Pages: 1212-1216
  • DOI: 10.1002/chem.201805800
  • Peer Reviewed
• [Journal Article] Three-Dimensional Sandwich Nanocubes Composed of 13-Atom Palladium Core and Hexakis-Carbocycle Shell (2018)
  • Author(s): Teramoto Masahiro、Iwata Kosuke、Yamaura Hiroshige、Kurashima Kenta、Miyazawa Koshi、Kurashige Yuki、Yamamoto Koji、Murahashi Tetsuro
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 40 Pages: 12682-12686
  • DOI: 10.1021/jacs.8b07430
  • Peer Reviewed
• [Presentation] 二座ホスフィン配位子を有するPd(I)錯体の合成とその反応性 (2019)
  • Author(s): 佐々木航汰, 山本浩二, 村橋哲郎
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Stereochemistry of Dinuclear Pd(I)-Pd(I) Addition and Elimination to/from 1,3-Diene (2019)
  • Author(s): Kota Sasaki, Koji Yamamoto, Tetsuro Murahashi
  • Organizer: 7th Asian Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] 1,3-ジエンに対するPd-Pd二核付加・脱離の立体制御 (2018)
  • Author(s): 佐々木航汰, 工藤瑛士, 山本浩二, 村橋哲郎
  • Organizer: 第65有機金属化学討論会
• [Presentation] E-Z Isomerization of 1,3-Dienes Mediated by Pd(I)-Pd(I) Dinuclear Complexes (2018)
  • Author(s): Eiji Kudo, Shiori Kawamata, Koji Yamamoto, Tetsuro Murahashi
  • Organizer: International CLS Forum on Photo and Catalytic Science for Sustainable Society
  • Int'l Joint Research
• [Presentation] I価Pd-Pd二核錯体を用いた1,3-ジエンのE→Z異性化反応 (2017)
  • Author(s): 工藤瑛士, 川俣志織, 山本浩二, 村橋哲郎
  • Organizer: 第64有機金属化学討論会