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2018 Fiscal Year Research-status Report

Binuclear Sandwiches of the Main Group Elements

Research Project

Project/Area Number 18K05137
Research InstitutionUniversity of Tsukuba

Principal Investigator

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

Project Period (FY) 2018-04-01 – 2021-03-31
Keywordscluster / group 14 element / group 13 element / binuclear sandwich / bis(pyramidane) / cyclobutadiene dianion / NMR spectroscopy / X-ray crystallography
Outline of Annual Research Achievements

The goal of this project is the development of synthetic approaches for the preparation of a novel class of the highly strained polyhedral clusters, bis- and poly(pyramidanes) and bis- and poly(housenes). Given their non-classical structures, such bi- and poly(nuclear) sandwiches of the main group elements are very interesting objects for fundamental studies, both experimental and computational, to reveal their peculiar structural features and unusual bonding situations. On the other hand, such polyhedral clusters could serve as very promising precursors for novel type of ceramics and nanostructural objects in material science.
In accord with the originally proposed plan, during the first year of the project we successfully synthesized a series of the neutral pyramidanes with the group 13 element at the apex of the square-pyramid. These compounds were readily prepared by the straightforward reaction of the corresponding cyclobutadiene dianion derivatives with the group 13 element halides EX3 (E = group 13 element). Reaction conditions (solvents, temperature, ratio of reagents) were optimized to maximize the yields of target pyramidanes. The structures of all synthesized pyramidanes were carefully studied both experimentally (X-ray, NMR) and computationally (high-level DFT calculations), and they were compared with the structures of the previously prepared pyramidanes of the group 14 elements.

Current Status of Research Progress
Current Status of Research Progress

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

Reason

During the first year of the project, our original plan was successfully fulfilled and the planned synthetic goals were realized. Thus, for example, a series of the target neutral borapyramidanes RB[C4(SiMe3)4] (R = Cl, Br, Ph, H) was quantitatively prepared by the coupling reaction of the readily available cyclobutadiene dianion dilithium salt {[C4(SiMe3)4](2-)}2Li+ with boron dihalides RBX2 (X = Cl, Br). All novel hybrid group 13/group 14 pyramidanes, namely borapyramidanes, were fully structurally characterized, and their apex-to-base bonding situations were comprehensively studied computationally.
Thus, during its first year, the project was running rather smoothly without any troubles and in accord with the originally proposed research plan and schedule.

Strategy for Future Research Activity

For the following second year of the project, we will attempt the synthesis of the bis(pyramidanes), as the bi(nuclear) sandwiches of the main group elements, as well as bis(housenes), utilizing previously synthesized mono(pyramidanes) and mono(housenes). Bis(pyramidanes) are expected to be prepared by the reductive dehalogenation of (halobora)pyramidane precursors with alkali or alkaline-earth metals, whereas bis(housenes) can be prepared by the reductive dehalogenation and coupling of the corresponding mono(housene) precursors with alkali or alkaline-earth metals. The structures and reactivity of these newly prepared clusters will be studied both experimentally and computationally, especially effects of substituents and skeletal atoms on the stability of these systems.

Causes of Carryover

For the first year of the project, the originally proposed amount was 1.600.000 yen, and actually 1.337.635 yen were used. It is caused by the changes in our original plan to purchase some equipment and reagents, because it was possible to perform our experiments without such equipment and reagents. Money remaining after the first year of the project, 262,365 yen, was transferred to the second year of the project, and will be used to purchase chemical reagents.

  • Research Products

    (11 results)

All 2019 2018

All Journal Article (4 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 4 results,  Open Access: 1 results) Presentation (7 results) (of which Int'l Joint Research: 5 results,  Invited: 1 results)

  • [Journal Article] [Pd(4-R3Si-IPr)(allyl)Cl], a Family of Silyl-Substituted Pd-NHC Complexes: Catalytic Systems for the Buchwald-Hartwig Amination2019

    • Author(s)
      N. Fukaya, T. Mizusaki, K. Hatakeyama, Y. Seo, Y. Inaba, K. Matsumoto, V. Ya. Lee,* Y. Takagi, J. Kuwabara, T. Kanbara, Y.-K. Choe, J.-C. Choi
    • Journal Title

      Organometallics

      Volume: 38 Pages: 376-384

    • DOI

      10.1021/acs.organomet.8b00757

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Tuning Philicity of Dichlorosilylene: Nucleophilic Behavior of the Dichlorosilylene-NHC Complex Cl2Si-IPr2019

    • Author(s)
      V. Ya. Lee,* S. Horiguchi, A. Sekiguchi, O. A. Gapurenko, T. N. Gribanova, V. I. Minkin, H. Gornitzka
    • Journal Title

      ACS Omega

      Volume: 4 Pages: 2902-2906

    • DOI

      10.1021/acsomega.8b03429

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] From Borapyramidane to Borole Dianion2018

    • Author(s)
      V. Ya. Lee,* H. Sugasawa, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin, H. Gornitzka, A. Sekiguchi
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 140 Pages: 6053-6056

    • DOI

      10.1021/jacs.8b03473

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Arsagermene, a compound with an As=Ge double bond2018

    • Author(s)
      V. Ya. Lee,* M. Kawai, O. A. Gapurenko, V. I. Minkin, H. Gornitzka, A. Sekiguchi
    • Journal Title

      Chem. Commun.

      Volume: 54 Pages: 10947-10949

    • DOI

      10.1039/c8cc05630g

    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Pyramidanes: Study of the Electronic Structures of Pyramidal Compounds and Their NMR Properties2019

    • Author(s)
      F. Takemura, V. Ya. Lee,* K. Morihashi
    • Organizer
      99th Annual Meeting of The Chemical Society of Japan, Japan, Kobe, Konan University, Japan
  • [Presentation] Cyclobutadiene Complexes of the s-, p-, and d-Block Elements2018

    • Author(s)
      V. Ya. Lee*
    • Organizer
      XIV Andrianov Conference “Organosilicon Compounds. Synthesis, Properties, Applications”, Moscow, Russia
    • Int'l Joint Research / Invited
  • [Presentation] Group 13 Element Silicon Pyramidanes2018

    • Author(s)
      O. A. Gapurenko, V. Ya. Lee,* R. M. Minyaev, V. I. Minkin
    • Organizer
      XIV Andrianov Conference “Organosilicon Compounds. Synthesis, Properties, Applications”, Moscow, Russia
    • Int'l Joint Research
  • [Presentation] R′E′[C4R4] (E′ = Group 15 or 13 Element) Cages and Clusters2018

    • Author(s)
      V. Ya. Lee,* H. Sugasawa, K. Ota, Y. Ito, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      15 International Symposium on Inorganic Ring Systems (IRIS-15), Kyoto, Japan
    • Int'l Joint Research
  • [Presentation] Pyramidanes: New Class of Cluster Compounds2018

    • Author(s)
      V. Ya. Lee,* O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      28 International Conference on Organometallic Chemistry (ICOMC 2018), Florence, Italy
    • Int'l Joint Research
  • [Presentation] Pyramidanes2018

    • Author(s)
      V. Ya. Lee,* O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14), Kyoto, Japan
    • Int'l Joint Research
  • [Presentation] The Study of Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes2018

    • Author(s)
      Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, N. Fukaya, V. Ya. Lee,* J.-C. Choi
    • Organizer
      48th Petroleum-Petrochemicals Symposium of JPI, Tokyo, Japan

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Published: 2019-12-27  

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