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2019 年度 実施状況報告書

Binuclear Sandwiches of the Main Group Elements

研究課題

研究課題/領域番号 18K05137
研究機関筑波大学

研究代表者

Lee Vladimir  筑波大学, 数理物質系, 講師 (90375410)

研究期間 (年度) 2018-04-01 – 2021-03-31
キーワードcluster / group 15 element / binuclear sandwich / pyramidane / bis(housene) / cyclobutadiene dianion / NMR spectroscopy / X-ray crystallography
研究実績の概要

The goal of the current project is the study of a novel class of the highly strained polyhedral clusters, pyramidanes and isomeric housenes. very interesting because of their unusual structures and bonding natures. They are also promising as precursors for novel type of polymers, ceramics and nanoobjects in material science. In accord with the initially proposed plan, during the second year of the project, we successfully synthesized first representatiave of bis(housenes) with antimony as the central elements. Moreover, cationic monopyramidanes with the apical heavier group 15 elements were also synthesized, isolated and structurally characterized. We also optimized the reaction conditions to maximize the yields of target products.

現在までの達成度 (区分)
現在までの達成度 (区分)

2: おおむね順調に進展している

理由

During the second year of the project, our original plan was successfully realized and initially planned synthetic goals were fully achieved.
Thus, the target bis(housene) [(Me3Si)4C4]E-E[C4(SiMe3)4] (E = Sb) was successfully prepared and fully structurally characterized, its unique bonding situation was computationally studied. In addition, we synthesized novel cationic pyramidanes with the heavier group 15 elements at the top of the square-pyramid. For preparation of the target bis(pyramidanes), we performed a detailed computational study to suggest synthetic strategies for their experimental realization. Thus, we can conclude that during its second year, our project was progressing rather smoothly without any troubles, in accord with the originally proposed research plan and schedule.

今後の研究の推進方策

For the following third year of the project, we will attempt synthesis of the bis(pyramidanes), as the binuclear sandwiches of the main group elements, by the reductive dehalogenation of the previously synthesized mono(halo)pyramidane precursors with alkali or alkaline-earth metals. Next, we will attempt synthesis of the most challenging poly(pyramidanes) and poly(housenes), starting from bis(pyramidanes) and bis(housenes) or from mono(pyramidanes) and mono(housenes). Structures, reactivity and potential applications of all novel clusters will be also comprehensively studied both experimentally (X-ray, NMR) and computationally (AIM, ELF). Particular attention will be paid to the systematic study of the influence of substituents and skeletal atoms on the stability of polyhedral systems.

次年度使用額が生じた理由

For the second year of the project, the originally required amount (including amount unused from previous fiscal year and indirect costs) was 1,440,696 yen (B), but actually 1,352,989 yen (A) were used. Such difference is caused by change in our original plan to purchase some chemical reagents, because it was possible to carry out our experiments without such reagents to achieve the research goals. Money remaining after the second year of the project, 87,707 yen (B-A), are transferred to the third year of the project, and will be used to purchase necessary chemical reagents.

  • 研究成果

    (14件)

すべて 2019

すべて 雑誌論文 (4件) (うち国際共著 4件、 査読あり 4件、 オープンアクセス 1件) 学会発表 (10件) (うち招待講演 5件)

  • [雑誌論文] Electronic structure and conformational isomerism of the digermene (tBu2MeSi)2Ge=Ge(SiMetBu2)2 as studied by temperature-dependent Raman and UV-Vis spectra and quantum-chemistry calculations.2019

    • 著者名/発表者名
      R. R. Aysin, S. S. Bukalov, L. A. Leites, V. Ya. Lee, A. Sekiguchi
    • 雑誌名

      J. Organomet. Chem.

      巻: 892 ページ: 18-23

    • DOI

      10.1016/j.jorganchem.2019.04.014

    • 査読あり / 国際共著
  • [雑誌論文] Theoretical Prediction for Synthetic Realization: Pyramidal Systems for Synthetic Realization ClE[E4R4] (E = B-Ga, E = C-Ge, R = SiMe3, SiMetBu2): A DFT Study2019

    • 著者名/発表者名
      O. A. Gapurenko, V. Ya. Lee, R. M. Minyaev, V. I. Minkin
    • 雑誌名

      Heteroatom Chem.

      巻: - ページ: 3659287

    • DOI

      10.1155/2019/3659287

    • 査読あり / オープンアクセス / 国際共著
  • [雑誌論文] [2 + 2] Cycloadduct of Titanium Silylidene and Benzonitrile2019

    • 著者名/発表者名
      V. Ya. Lee, S. Horiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin, H. Gornitzka, A. Sekiguchi
    • 雑誌名

      Eur. J. Inorg. Chem.

      巻: - ページ: 4224-4227

    • DOI

      10.1002/ejic.201900601

    • 査読あり / 国際共著
  • [雑誌論文] Tricoordinate Silicon Cations (Silylium Ions) (invited)2019

    • 著者名/発表者名
      V. Ya. Lee
    • 雑誌名

      Russ. Chem. Rev.

      巻: 88 ページ: 351-369

    • DOI

      10.1070/RCR4868

    • 査読あり / 国際共著
  • [学会発表] Schrock-Type Silylidenes and Germylidenes2019

    • 著者名/発表者名
      V. Ya. Lee
    • 学会等名
      2nd International Conference of Hyper- and Hypocoordinated Compounds of the Group 14 Elements, France, Rennes, June 19-21
    • 招待講演
  • [学会発表] Pyramidane: The Smallest Member of the Fenestranes Family2019

    • 著者名/発表者名
      V. Ya. Lee, O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • 学会等名
      5th EuChemS Inorganic Chemistry Conference (EICC-5), Russia, Moscow, June 24-28
    • 招待講演
  • [学会発表] Cyclobutadiene Complexes of the s-, p-, and d-Block Elements2019

    • 著者名/発表者名
      V. Ya. Lee
    • 学会等名
      13th International Conference on Heteroatom Chemistry (ICHAC 2019), Czech Republic, Prague, June 30-July 5
    • 招待講演
  • [学会発表] Group 4 Metal Germylidenes (and Related Complexes)2019

    • 著者名/発表者名
      V. Ya. Lee, R. Sakai, T. Yokoyama, S. Aoki, K. Takanashi, A. Sekiguchi
    • 学会等名
      16th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (GTL-2019), Japan, Saitama, September 1-6
  • [学会発表] Alkene Metathesis: Silicon and Germanium Versions2019

    • 著者名/発表者名
      V. Ya. Lee
    • 学会等名
      XXIth Mendeleev Congress on General and Applied Chemistry, Saint-Petersburg, Russia, September 9-13
    • 招待講演
  • [学会発表] Pyramidanes2019

    • 著者名/発表者名
      V. Ya. Lee
    • 学会等名
      Visiting Professor at the Graz University of Technology, Graz, Austria, 18-28 October
    • 招待講演
  • [学会発表] Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes2019

    • 著者名/発表者名
      Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, K. Matsumoto, J.-C. Choi, N. Fukaya
    • 学会等名
      8th JACI/GSC Symposium 2019(Japan Association for Chemical Innovation/Green and Sustainable Chemistry), Tokyo, Tokyo International Forum, 24-25 June
  • [学会発表] Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes2019

    • 著者名/発表者名
      Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, K. Matsumoto, J.-C. Choi, N. Fukaya
    • 学会等名
      66th Symposium on Organometallic Chemistry, Tokyo, Tokyo Metropolitan University, 14-16 September
  • [学会発表] Catalytic Performance of Silyl Group-Substituted N-Heterocyclic Carbene Complexes2019

    • 著者名/発表者名
      Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, Y.-K. Choe, K. Matsumoto, J.-C. Choi, N. Fukaya
    • 学会等名
      100th Annual Meeting of The Chemical Society of Japan, Noda, Tokyo University of Science, 22-25 March
  • [学会発表] Computational Chemical Verification of Activation of [R3Si-IPr]Pd Catalyst Precursor in Suzuki-Miyaura Cross-Coupling Reaction2019

    • 著者名/発表者名
      J. Fujiwara, Y. Ozaki, V. Ya. Lee, T. Matsui, K. Morihashi
    • 学会等名
      100th Annual Meeting of The Chemical Society of Japan, Noda, Tokyo University of Science, 22-25 March

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公開日: 2021-01-27  

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