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2021 Fiscal Year Research-status Report

反芳香族B,N-カルベンσ配位子の開発と常磁性/アニオン性金錯体の合成と物性解明

Research Project

Project/Area Number 21K05099
Research InstitutionHiroshima University

Principal Investigator

SHANG RONG  広島大学, 先進理工系科学研究科(理), 助教 (70754216)

Project Period (FY) 2021-04-01 – 2024-03-31
KeywordsAurate / Carbene / boron / redox active ligand
Outline of Annual Research Achievements

Stabilization of low oxidation gold anions as aurate or auride by organic ligands has long been a synthetic challenge, owing to the proneness for low-valent gold centers to cluster. Stabilization of highly-reduced gold complexes by π-modulating redox active ligand has only been achieved by cyclic (amino)(alkyl)carbene (CAAC). This work reports a simple modular synthesis of a boron, nitrogen-containing heterocyclic carbene (ClBNC) at a gold(I) center. These complexes showed a highly π-withdrawing character in the neutral 4π B,N-heterocyclic carbene (BNC) moiety and its reduced form showed π-donating properties to the gold(I) fragment, showcasing the first cyclic carbene ligand that allows electronic tunability between π-withdrawing and π-donating properties.

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

The complexation chemistry of the (tri-tert-butyl)azadiboriridine with gold(I) complexes, Au(L)Cl yielded borylgold(I)borane and borenium boryl-aurate complexes, which reacted with CNtBu to form a boron-containing heterocyclic (bora)iminyl ligand (ClBNC) in high-yields. Overall, the ClBNC ligand in neutral [(ClBNC)Au(PMe3)] complexes features a highly π-withdrawing carbene center while carrying a negative charge from borate moiety. Its ability to adopt both π-withdrawing and π-donating properties through redox chemistry makes them a great candidate for modulate the electronic states of the coordinated metal fragment, allowing the isolation of the first carbene-aurate complex.

Strategy for Future Research Activity

The isolation of the 2-electron reduction product lithium aurate revealed our anticipated strategy for π-modulation is successful. In the future, three aspects will be pursued to further explore the potential of main-group π-modulating ligands to redox properties of transition metal complexes. Firstly, we will expand the reduction chemistry to amino- and Mesityl-derivatives. Their neutral (ClBNC)AuL precursors have been successfully obtained. Secondly, we are extending similar concept to diboron-phosphide (BNP) ligand. With two more electron at phosphine atom, it is a π-donor in contrast to current π-accepting BNC carbene ligands. Its oxidation will be investigated. Lastly, we are also extending this to all carbon multi-dentate ligands.

Causes of Carryover

Due to COVID restrictions on traveling and remote work, part of budget could not be used. This will be used in purchases of chemicals required for this project, renewal of laboratory equipments such as magnetic stirrers, glassware as well as international travel for further collaborations involved in this project.

  • Research Products

    (10 results)

All 2022 2021 Other

All Int'l Joint Research (2 results) Journal Article (4 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 4 results,  Open Access: 1 results) Presentation (4 results) (of which Int'l Joint Research: 3 results,  Invited: 1 results)

  • [Int'l Joint Research] Department of Chemistry,/Division of Natural and Exact Sciences,/University of Guanajuato(メキシコ)

    • Country Name
      MEXICO
    • Counterpart Institution
      Department of Chemistry,/Division of Natural and Exact Sciences,/University of Guanajuato
  • [Int'l Joint Research] Centro Conjunto de Investigacion/en Quimica Sustentable UAEM-UNAM/Unidad San Cayetano(メキシコ)

    • Country Name
      MEXICO
    • Counterpart Institution
      Centro Conjunto de Investigacion/en Quimica Sustentable UAEM-UNAM/Unidad San Cayetano
  • [Journal Article] Near-infrared absorbing (>700 nm) aza-BODIPYs by freezing the rotation of the aryl groups2022

    • Author(s)
      Wang Yanyan、Zhang Dongxiang、Xiong Kangming、Shang Rong、Jiang Xin-Dong
    • Journal Title

      Chinese Chemical Letters

      Volume: 33 Pages: 115~122

    • DOI

      10.1016/j.cclet.2021.06.083

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis and Isolation of an Anionic Bis(dipyrido-annulated) N-Heterocyclic Carbene CCC-Pincer Iridium(III) Complex by Facile C-H Bond Activation2021

    • Author(s)
      Nakanishi Kazuki、Jimenez-Halla J. Oscar. C.、Yamazoe Seiji、Nakamoto Masaaki、Shang Rong、Yamamoto Yohsuke
    • Journal Title

      Inorganic Chemistry

      Volume: 60 Pages: 9970~9976

    • DOI

      10.1021/acs.inorgchem.1c01236

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Spherand complexes with Li+ and Na+ ions in the gas phase: encapsulation structure and characteristic unimolecular dissociation2021

    • Author(s)
      Kida Motoki、Wada Kanako、Muramatsu Satoru、Shang Rong、Yamamoto Yohsuke、Inokuchi Yoshiya
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 23 Pages: 25029~25037

    • DOI

      10.1039/d1cp03336k

    • Peer Reviewed
  • [Journal Article] Proton to hydride umpolung at a phosphonium center via electron relay: a new strategy for main-group based water reduction2021

    • Author(s)
      Oishi Takumi、Lugo-Fuentes Leonardo I.、Jing Yichuan、Jimenez-Halla J. Oscar C.、Barroso-Flores Joaquin、Nakamoto Masaaki、Yamamoto Yohsuke、Tsunoji Nao、Shang Rong
    • Journal Title

      Chemical Science

      Volume: 12 Pages: 15603~15608

    • DOI

      10.1039/d1sc05135k

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Developments of main-group ligands for Transition Metal Complexes: a journey of unexpected reactivity2021

    • Author(s)
      Rong Shang
    • Organizer
      E Quimica Inorganica (EQI, Mexican Meeting of Inorganic Chemistry
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis Towards Chiral π-Conjugated Iridium Metallacycles2021

    • Author(s)
      Rong Shang, Kazuki Nakanishi, J. Oscar C. Jimenez-Halla, Seiji Yamazoe, Masaaki Nakamoto, Hiroto Yoshida and Yohsuke Yamamoto
    • Organizer
      Symposium on Molecular Chirality 2021 (Hiroshima)
    • Int'l Joint Research
  • [Presentation] Dipyrido-Annulated N-Heterocyclic Carbene-Based Pincer Ligands And Their Complexation To Late Transition Metals2021

    • Author(s)
      Rong Shang, Kazuki Nakanishi, Sihan Zhang, Naoto Maeta, and Yohsuke Yamamoto, Seiji Yamazoe
    • Organizer
      The 2020 International Chemical Congress of Pacific Basin Societies (Pacifichem 2021) #222
    • Int'l Joint Research
  • [Presentation] Synthesis and Characterization of an Lithium (BNC-)Aurate Complex by Using a 4π Boron, Nitrogen-Containing Heterocyclic Carbene (BNC) as a Redox Non-innocent Ligand2021

    • Author(s)
      Rong Shang, Yoshitaka Kimura, Leonardo I. Lugo-Fuentes, Souta Saito, J. Oscar C. Jimenez-Halla, Joaquin Barroso- Flores, Massaki Nakamoto, Yohsuke Yamamoto, Hiroto Yoshida
    • Organizer
      第67回有機金属化学討論会

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Published: 2022-12-28  

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