Development of manganese-catalyzed olefin metathesis reaction

• Project/Area Number: 18K14230
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Okinawa Institute of Science and Technology Graduate University
• Principal Investigator: Takebayashi Satoshi 沖縄科学技術大学院大学, サイエンステクノロジーグループ, サイエンス・テクノロジーアソシエイト (10609283)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); 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)
• Keywords: コバルト / NHC配位子 / カルボニル / 二核錯体 / 水素分子活性化 / ホモリシス / 核磁気分光法 / ヒドロフォルミル化 / メタロラジカル / オレフィンメタセシス / マンガン触媒

Outline of Final Research Achievements

In this research, we aimed at developing manganese-catalyzed olefin metathesis reaction. We could not discover the aimed reaction; however we obtained the following results using iron and cobalt complexes. 1. The first isolation of cobalt(0) carbonyl complex and understanding of its reactivity towards hydrogen. 2. The first direct observation of chemical bond homolysis using binuclear cobalt(0) complexes. 3. Discovery of iron-catalyzed olefin metathesis reaction.

Academic Significance and Societal Importance of the Research Achievements

本研究で明らかにしたコバルト錯体の反応性はこれまでに知られていなかったコバルト（０）ラジカルの反応性を明らかにするものであり、学術的な意義がある。また、ここで得られた知見はコバルト錯体を用いた触媒反応の開発や二核金属錯体を用いた触媒反応、新規機能性物質の開発に応用できるという点で将来的に社会の発展に貢献する。

Research Products

• [Int'l Joint Research] Arbuzov Institute(ロシア連邦)
• [Int'l Joint Research] Weizmann Institute of Science(イスラエル)
• [Int'l Joint Research] Arbuzov Institute(ロシア連邦)
• [Journal Article] Iron-catalysed ring opening metathesis polymerization of olefins and mechanistic studies (2022)
  • Author(s): Satoshi Takebayashi, Mark A. Iron, Moran Feller, Orestes Rivada-Wheelaghan, Gregory Leitus, Yael Diskin-Posner, Linda J. W. Shimon, Liat Avram, Raanan Carmieli, Sharon G. Wolf, Ilit Cohen-Ofri, Rajashekharayya A. Sanguramath, Roy Shenhar, Moris Eisen, and David Milstein
  • Journal Title: Nature Catalysis Volume: Accepted
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] [Co(NHC)(CO)3]: Isolation and Reactivity Study of a Model 17-Electron Species in the Oxo Process (2021)
  • Author(s): Takebayashi Satoshi、Fayzullin Robert R.
  • Journal Title: Organometallics Volume: 40 Issue: 4 Pages: 500-507
  • DOI: 10.1021/acs.organomet.0c00765
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Direct EXSY NMR observation of reversible Co-Co bond homolysis (2022)
  • Author(s): 竹林智司
  • Organizer: The 102nd CSJ annual meeting
• [Presentation] Isolation of Mononuclear [Co(ligand)(CO)3] Metalloradicals and Its H2 Activation Mechanisms (2021)
  • Author(s): 竹林智司
  • Organizer: Pacifichem 2021
  • Int'l Joint Research
• [Presentation] Co(NHC)(CO)3]ラジカルの単離とその水素分子活性化反応機構 (2021)
  • Author(s): Takebayashi, S. Fayzullin, R.
  • Organizer: The 101st CSJ annual meeting
• [Presentation] Isolation and Reactivity Study of 17-electron Metalloradical [Co(NHC)(CO)3]. (2020)
  • Author(s): Takebayashi, S. Fayzullin, R.
  • Organizer: The 100th CSJ annual meeting
• [Remarks] Satoshi Takebayashi
  • URL: https://groups.oist.jp/stg/satoshi-takebayashi
• [Remarks]
  • URL: https://groups.oist.jp/stg/satoshi-takebayashi
• [Remarks] Science and Technology Group, Annual Reports
  • URL: https://groups.oist.jp/stg/annual-reports