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2016 年度 実施状況報告書

Pyramidal Structures: New Type of Cluster Compounds

研究課題

研究課題/領域番号 15K05413
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) 2015-04-01 – 2018-03-31
キーワードcluster / group 14 element / group 15 element / housene / pyramidane / cyclobutadiene dianion / NMR spectroscopy / X-Ray crystallography
研究実績の概要

The goal of this project is the development of new synthetic approaches for the preparation of a novel class of the highly strained polyhedral clusters, pyramidanes, pyramidal compounds of the heavier main group elements.
Given their non-classical structures, pyramidanes are very interesting objects for the fundamental studies, both experimental and computational, to reveal their peculiar structural features and unusual bonding situations. On the other hand, pyramidanes could serve as very promising precursors for novel type of ceramics and nanostructural objects in material science.
In accord with the initially proposed plan, during the second year of the project we successfully synthesized a series of the cationic pyramidanes with the heavier group 15 element (P, Sb, Bi) at the apex of the square-pyramid. These target compounds were prepared by the straightforward reaction of the readily available cyclobutadiene and tetrasilacyclobutadiene dianion derivatives with the group 15 element halides EX3 (E = group 15 element). Reaction conditions (solvents, temperature, ratio of reagents) were optimized to maximize the yields of target pyramidanes. The structures of all pyramidanes were thoroughly studied both experimentally (X-Ray, NMR) and computationally (high-level DFT calculations), and then compared with those of their heavier group 14 element analogues.

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, all plans were successfully fulfilled and all synthetic targets were realized. As was originally planned, the target cationic pyramidanes were prepared by the coupling reaction of the readily available cyclobutadiene dianion derivatives and group 15 element halides followed by the oxidative dehalogenation of the initially formed (halo)housenes. Accordingly, a whole series of the cationic hybrid group 14/group 15 element pyramidanes E'[E4(SiR3)4] (E' = group 15 element, E = group 14 element) was synthesized, fully structurally characterized, and comprehensively computationally studied.
Thus, during its second year, the project was running very smoothly with no any troubles, according to the originally proposed research plans and schedule.

今後の研究の推進方策

During the third year of the project, we will focus on the synthesis of anionic hybrid group 13/group 14 element pyramidanes E'[E4(SiR3)4] (E' = group 13 element, E = group 14 element) which could be prepared by the reaction of cyclobutadiene dianion derivatives and group 13 element halides followed by the reductive dehalogenation of the initially formed (halo)housenes. The structures of these anionic pyramidanes will be thoroughly studied, both experimentally and theoretically.
Finally, the reactivity of all prepared pyramidanes (neutral, cationic, anionic) will be investigated towards their practical use in the synthetic organometallic chemistry and their application in material science as the promising precursors for the new advanced materials.

次年度使用額が生じた理由

For the second year of the project, the originally proposed and actually used money to purchase equipment and chemical reagents were nearly the same, 900000 yen vs. 863470 yen. However, some money remaining after the first year of the project were transferred to the second year (955385 yen) These money were partially used for the conference traveling to attend very important major international symposiums abroad where invited plenary lectures were delivered. That is why the amount for traveling is greater than was originally planned.
After the second year of the project, the remaining amount was 266621 yen.

次年度使用額の使用計画

The amount of money remaining after the second year of the project will be used within the third year of the project to purchase chemical reagents necessary to fulfill the research goals and perform the required experimental work. The successful realization of the research plan of the third year of the project requires the use of such reagents.

  • 研究成果

    (14件)

すべて 2017 2016 その他

すべて 国際共同研究 (1件) 雑誌論文 (5件) (うち国際共著 5件、 査読あり 5件、 謝辞記載あり 4件) 学会発表 (7件) (うち国際学会 5件、 招待講演 2件) 図書 (1件)

  • [国際共同研究] Southern Federal University(ロシア連邦)

    • 国名
      ロシア連邦
    • 外国機関名
      Southern Federal University
  • [雑誌論文] The Study of Bonding in Pyramidanes [(Me3Si)4C4]E (E = Ge, Sn, Pb) by Optical (Raman, UV-vis) Spectroscopy and Quantum-Chemical Methods2017

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

      J. Mol. Struct.

      巻: 1130 ページ: 775-780

    • DOI

      10.1016/j.molstruc.2016.11.001

    • 査読あり / 国際共著
  • [雑誌論文] Pyramidanes: The Covalent Form of the Ionic Compounds2016

    • 著者名/発表者名
      V. Ya. Lee, O. A. Gapurenko, Y. Ito, T. Meguro, H. Sugasawa, A. Sekiguchi, R. M. Minyaev, V. I. Minkin, R. H. Herber, H. Gornitzka
    • 雑誌名

      Organometallics

      巻: 35 ページ: 346-356

    • DOI

      10.1021/acs.organomet.5b00924

    • 査読あり / 国際共著 / 謝辞記載あり
  • [雑誌論文] A Cationic Phosphapyramidane2016

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

      Chemitsry - A European Journal

      巻: 22 ページ: 17585-17589

    • DOI

      10.1002/chem.201604480

    • 査読あり / 国際共著 / 謝辞記載あり
  • [雑誌論文] Group 14 element cationic pentagonal-pyramidal complexes Ea[η5-Eb5(SiMe3)5]+ (Ea = Si-Pb, Eb = Si, Ge): A quantum-chemical study2016

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

      Phosphorus, Sulfur, and Silicon

      巻: 191 ページ: 609-612

    • DOI

      10.1080/10426507.2015.1128917

    • 査読あり / 国際共著 / 謝辞記載あり
  • [雑誌論文] [2+2] Cycloaddition of the Schrock titanium silylidene and acetylene2016

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

      Russian Chemical Bulletin, International Edition

      巻: 65 ページ: 1139-1141

    • DOI

      10.1007/s11172-016-1425-9

    • 査読あり / 国際共著 / 謝辞記載あり
  • [学会発表] Synthesis of Pyramidanes with the Group 13 Element at the Apex2017

    • 著者名/発表者名
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • 学会等名
      97th Annual Meeting of The Chemical Society of Japan
    • 発表場所
      Keio University (Yokohama), Kanagawa prefecture, Japan
    • 年月日
      2017-03-16 – 2017-03-19
  • [学会発表] Reactivity of the Cyclobutadiene Dianion Dilithium Salt Toward the Group 13 Element Halides2016

    • 著者名/発表者名
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • 学会等名
      20th Symposium of the Society of Silicon Chemistry Japan
    • 発表場所
      Aki Grand Hotel (Hiroshima), Hiroshima prefecture, Japan
    • 年月日
      2016-10-07 – 2016-10-08
  • [学会発表] Anti Van’t Hoff-Le Bel Configurations as the Main Group Elements2016

    • 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
      Mendeleev Congress on General and Applied Chemistry
    • 発表場所
      Ekaterinburg Expo International Exhibition center (Ekaterinburg), Russian Federation
    • 年月日
      2016-09-26 – 2016-09-30
    • 国際学会 / 招待講演
  • [学会発表] Pyramidal Structures of Group 13 and 15 Elements with Silicon Basal Rings2016

    • 著者名/発表者名
      O. A. Gapurenko, V. Ya. Lee, R. M. Minyaev, V. I. Minkin, A. Sekiguchi
    • 学会等名
      Mendeleev Congress on General and Applied Chemistry
    • 発表場所
      Ekaterinburg Expo International Exhibition center (Ekaterinburg), Russian Federation
    • 年月日
      2016-09-26 – 2016-09-30
    • 国際学会
  • [学会発表] Inverted Tetrahedral Geometry at the Heavier Group 14 Elements: Pyramidanes and Propellanes2016

    • 著者名/発表者名
      V. Ya. Lee, O. A. Gapurenko, Y. Ito, Y. Meguro, H. Sugasawa, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • 学会等名
      15th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-2016)
    • 発表場所
      University of Pardubice (Pardubice), Czech Republic
    • 年月日
      2016-08-28 – 2016-09-02
    • 国際学会 / 招待講演
  • [学会発表] Group 14 Element Pyramidanes2016

    • 著者名/発表者名
      O. A. Gapurenko, R. M. Minyaev, V. I. Minkin, V. Ya. Lee, A. Sekiguchi
    • 学会等名
      15th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-2016)
    • 発表場所
      University of Pardubice (Pardubice), Czech Republic
    • 年月日
      2016-08-28 – 2016-09-02
    • 国際学会
  • [学会発表] Phosphapyramidane2016

    • 著者名/発表者名
      V. Ya. Lee, O. A. Gapurenko, H. Sugasawa, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • 学会等名
      21st International Conference on Phosphorus Chemistry (ICPC-XXI)
    • 発表場所
      Hotel Korston (Kazan), Russian Federation
    • 年月日
      2016-06-05 – 2016-06-10
    • 国際学会
  • [図書] Organic Redox Systems: Synthesis, Properties, and Applications2016

    • 著者名/発表者名
      V. Ya. Lee, A. Sekiguchi
    • 総ページ数
      616
    • 出版者
      Wiley

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公開日: 2018-01-16   更新日: 2022-02-16  

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