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Construction of tetrahedral chiral-at-metal complexes towards asymmetric light-driven redox catalysis

Research Project

Project/Area Number 22KJ0852
Project/Area Number (Other) 22J12312 (2022)
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeMulti-year Fund (2023)
Single-year Grants (2022)
Section国内
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionThe University of Tokyo

Principal Investigator

LIU Yuanfei  東京大学, 理学系研究科, 特別研究員(PD)

Project Period (FY) 2023-03-08 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2023: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2022: ¥900,000 (Direct Cost: ¥900,000)
Keywordschiral-at-metal / spontaneous resolution / conglomerate crystal / hydrogen bonds / carbon-carbon cleavage / nickel / cobalt / tetrahedral geometry / redox-active
Outline of Research at the Start

Chiral-at-metal complexes are complexes which have a stereogenic metal center and show promises as chiral catalysts and optical materials. My research is to develop synthetic method to obtain enantiopure redox-active tetrahedral chiral-at-metal complexes and apply them to asymmetric reactions.

Outline of Annual Research Achievements

The racemic tetrahedral chiral-at-nickel(II) complex, [NiIIL(ClLi(thf)2)] was synthesized and well characterized. Crystallization via liquid-liquid diffusion at -18 °C caused spontaneous resolution, which separated S/R isomers into different conglomerate crystals. By examining crystal structure of crystals, I found that nickel complexes of the same configuration extended into chiral helix via weakly interacting hydrogen bonds. Then the chiral helix of the same handedness further extended into 3D superstructure, eventually forming conglomerate crystals.
The racemic tetrahedral chiral-at-cobalt(II) complex was synthesized and well characterized. During the ligand exchange trials, it was found that by mixing the cobalt complex, 1,2-(dinaphth-1-yl)-1,2-ethlenediamine, AgClO4 and heating at 50 °C for 24 h, 12% of 1-naphthylaldehyde was obtained (NMR yield). Also, upon crystallization, [CoIIL(1-naphthylaldehyde)] crystals were obtained. Compared with control experiments, this result indicated that carbon-carbon bond cleavage of the 1,2-diamine would take place in the presence of the cobalt complex.

Report

(2 results)
  • 2023 Annual Research Report
  • 2022 Annual Research Report
  • Research Products

    (7 results)

All 2023 2022

All Journal Article (2 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 2 results) Presentation (5 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Temperature-Dependent Spontaneous Resolution of a Tetrahedral Chiral-at-Nickel(II) Complex under Supramolecular Control2023

    • Author(s)
      Yuanfei Liu, Hitoshi Ube,* Kenichi Endo, Mitsuhiko Shionoya*
    • Journal Title

      ACS Org. Inorg. Au.

      Volume: 3 Issue: 6 Pages: 371-376

    • DOI

      10.1021/acsorginorgau.3c00026

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Precise Design of Chiral-at-Metal Complexes: Synthesis and Catalytic Functions of a Tetrahedral Chiral Zinc Complex2022

    • Author(s)
      Endo Kenichi、Liu Yuanfei、Ube Hitoshi、Nagata Koichi、Shionoya Mitsuhiko
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 80 Issue: 5 Pages: 498-505

    • DOI

      10.5059/yukigoseikyokaishi.80.498

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2022-05-01
    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Temperature-Dependent Spontaneous Resolution of a Tertahedral Chiral-at-Nickel(II) Complex2023

    • Author(s)
      Yuanfei Liu, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      錯体化学会第73回討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] Temperature-Dependent Spontaneous Resolution of a Tertahedral Chiral-at-Nickel(II) Complex2023

    • Author(s)
      Yuanfei Liu, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      第13回サブウェイセミナー
    • Related Report
      2023 Annual Research Report
  • [Presentation] Construction of Redox-active Tetrahedral Chiral-at-Metal Complexes with Only Achiral Ligands2022

    • Author(s)
      Yuanfei Liu, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      第13回低温センター研究交流会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Optical resolution of a tetrahedral chiral-at-nickel(II) complex with only achiral ligands2022

    • Author(s)
      Yuanfei Liu, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      8th Asian Conference on Coordination Chemistry
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Construction of Optically Pure Tetrahedral Chiral-at-Metal Catalysts Using Only Achiral Ligands2022

    • Author(s)
      Yuanfei Liu, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      JSPS 14th HOPE Meeting with Nobel Laureates
    • Related Report
      2022 Annual Research Report

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Published: 2022-04-28   Modified: 2024-12-25  

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