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Pyramidal Structures: New Type of Cluster Compounds

Research Project

Project/Area Number 15K05413
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Organic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

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

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywordscluster / pyramidane / housene / cyclobutadiene dianion / group 14 element / group 15 element / group 13 element / X-ray crystallography / NMR spectroscopy / X-Ray crystallography
Outline of Final Research Achievements

Pyramidanes are among the most challenging synthetic targets for organic chemistry, which are still eluded their synthetic realization despite their evident interest and importance. Neither parent pyramidane C[C4H4] nor its derivatives have ever been isolated and characterized. In the current project, we proposed and developed totally new synthetic strategy for the preparation of such elusive species by the straightforward reaction of the readily available cyclobutadiene dianion derivatives (developed in our group) with the main group elements halides. Using this simple approach, we succeeded in the synthesis of a whole series of the neural group 14 element pyramidanes and their isoelectronic cationic counterparts featuring heavier group 15 element at the top of the square pyramid. All newly isolated pyramidanes were undoubtedly structurally characterized.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (42 results)

All 2017 2016 2015 Other

All Int'l Joint Research (2 results) Journal Article (11 results) (of which Int'l Joint Research: 8 results,  Peer Reviewed: 11 results,  Acknowledgement Compliant: 6 results,  Open Access: 1 results) Presentation (25 results) (of which Int'l Joint Research: 11 results,  Invited: 9 results) Book (4 results)

  • [Int'l Joint Research] Southern Federal University(ロシア連邦)

    • Related Report
      2016 Research-status Report
  • [Int'l Joint Research] Southern Federal University(ロシア連邦)

    • Related Report
      2015 Research-status Report
  • [Journal Article] The study of Bonding in Pyramidanes [(Me3Si)4C4]E (E = Ge, Sn, Pb) by Optical (Raman, UV-vis) Spectroscopy and Quantum-chemical Methods.2017

    • Author(s)
      L. A. Leites, R. R. Aysin, S. S. Bukalov, V. Ya. Lee, H. Sugasawa, A. Sekiguchi
    • Journal Title

      J. Mol. Struct.

      Volume: 1130 Pages: 775-780

    • DOI

      10.1016/j.molstruc.2016.11.001

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Hybrid Group 15(E15)-Group 14(E14) Element Cationic Pyramidal Structures E15[E144(SiR3)4]+: A DFT study.2017

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

      Tetrahedron Letters

      Volume: 58 Issue: 21 Pages: 2054-2057

    • DOI

      10.1016/j.tetlet.2017.04.040

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Bis(stibahousene).2017

    • Author(s)
      V. Ya. Lee, K. Ota, Y. Ito, O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin, H. Gornitzka
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 39 Pages: 13897-13902

    • DOI

      10.1021/jacs.7b07712

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Pyramidanes: The Covalent Form of the Ionic Compounds.2016

    • Author(s)
      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
    • Journal Title

      Organometallics

      Volume: 35 Issue: 3 Pages: 346-356

    • DOI

      10.1021/acs.organomet.5b00924

    • Related Report
      2016 Research-status Report 2015 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] A Cationic Phosphapyramidane.2016

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

      Chem. Eur. J.

      Volume: 22 Issue: 49 Pages: 17585-17589

    • DOI

      10.1002/chem.201604480

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Group 14 Element Cationic Pentagonal-Pyramidal Complexes Ea[η5-Eb5(SiMe3)5]+ (Ea = Si;Pb, Eb = Si, Ge): A Quantum-Chemical Study.2016

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

      Phosphorus, Sulfur and Silicon

      Volume: 191 Issue: 4 Pages: 609-612

    • DOI

      10.1080/10426507.2015.1128917

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] [2+2] Cycloaddition of the Schrock titanium silylidene and acetylene2016

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, V. I. Minkin, S. Horiguchi, A. Sekiguchi
    • Journal Title

      Russian Chemical Bulletin, International Edition

      Volume: 65 Issue: 4 Pages: 1139-1141

    • DOI

      10.1007/s11172-016-1425-9

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] A Schrock-Type Germylene Complex: (η5-C5H4Et)2(PMe3)Hf=Ge(SiMetBu2)2.2015

    • Author(s)
      Norio Nakata, Shinji Aoki, Vladimir Ya. Lee, Akira Sekiguchi
    • Journal Title

      Organometallics

      Volume: 34 Issue: 11 Pages: 2699-2699

    • DOI

      10.1021/om501134a

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pentagermapyramidane: Crystallizing the “Transition State” Structure.2015

    • Author(s)
      Vladimir Ya. Lee, Yuki Ito, Olga A. Gapurenko, Akira Sekiguchi, Vladimir I. Minkin, Ruslan M. Minyaev, Heinz Gornitzka
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 54 Issue: 19 Pages: 5654-5654

    • DOI

      10.1002/anie.201500731

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] From a Si3-Cyclopropene to a Si3S-Bicyclo[1.1.0]butane to a Si3S-Cyclopropene to a Si3S2-Bicyclo[1.1.0]butane: Back-and-Forth, and In-Between.2015

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

      Angew. Chem. Int. Ed.

      Volume: 54 Issue: 47 Pages: 14118-14118

    • DOI

      10.1002/anie.201506625

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] 1,1-Dilithiosilanes, 1,1-dilithiogermanes and 1,1-dilithiostannanes and related compounds: organometallic reagents of the new generation.2015

    • Author(s)
      V. Ya. Lee, A. Sekiguchi
    • Journal Title

      Mendeleev Commun.

      Volume: 25 Issue: 3 Pages: 161-161

    • DOI

      10.1016/j.mencom.2015.05.001

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] Synthesis of Pyramidanes with the Group 13 Element at the Apex2017

    • Author(s)
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      97th Annual Meeting of The Chemical Society of Japan
    • Place of Presentation
      Keio University (Yokohama), Kanagawa prefecture, Japan
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Pyramidanes2017

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-19) (Jeju, South Korea)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Pyramidanes2017

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      22nd International Conference on Organometallic Chemistry (EuCOMC-XXII) (Amsterdam, The Netherlands)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Pyramidanes2017

    • Author(s)
      V. Ya. Lee
    • Organizer
      Russian-French Workshop on Hyper- and Hypocoordinated Compounds of the Group 14 Elements (Moscow, Russia)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Pyramidanes2017

    • Author(s)
      V. Ya. Lee
    • Organizer
      VII International Symposium “Chemistry and Chemical Education” (Vladivostok, Russia)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Pyramidanes2017

    • Author(s)
      V. Ya. Lee
    • Organizer
      “INEOS OPEN CUP” Conference (Moscow, Russia)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Invited Seminars2017

    • Author(s)
      V. Ya. Lee
    • Organizer
      University of Muenster and University of Goettingen (Germany)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Pyramidanes with the Group 13 Element at the Apex2017

    • Author(s)
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      97th Annual Meeting of The Chemical Society of Japan (Yokohama, Japan)
    • Related Report
      2017 Annual Research Report
  • [Presentation] Reactivity of the Cyclobutadiene Dianion Dilithium Salt Toward the Group 13 Element Halides2016

    • Author(s)
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      20th Symposium of the Society of Silicon Chemistry Japan
    • Place of Presentation
      Aki Grand Hotel (Hiroshima), Hiroshima prefecture, Japan
    • Year and Date
      2016-10-07
    • Related Report
      2016 Research-status Report
  • [Presentation] Anti Van’t Hoff-Le Bel Configurations as the Main Group Elements2016

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      Mendeleev Congress on General and Applied Chemistry
    • Place of Presentation
      Ekaterinburg Expo International Exhibition center (Ekaterinburg), Russian Federation
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Pyramidal Structures of Group 13 and 15 Elements with Silicon Basal Rings2016

    • Author(s)
      O. A. Gapurenko, V. Ya. Lee, R. M. Minyaev, V. I. Minkin, A. Sekiguchi
    • Organizer
      Mendeleev Congress on General and Applied Chemistry
    • Place of Presentation
      Ekaterinburg Expo International Exhibition center (Ekaterinburg), Russian Federation
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Inverted Tetrahedral Geometry at the Heavier Group 14 Elements: Pyramidanes and Propellanes2016

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, Y. Ito, Y. Meguro, H. Sugasawa, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      15th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-2016)
    • Place of Presentation
      University of Pardubice (Pardubice), Czech Republic
    • Year and Date
      2016-08-28
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Group 14 Element Pyramidanes2016

    • Author(s)
      O. A. Gapurenko, R. M. Minyaev, V. I. Minkin, V. Ya. Lee, A. Sekiguchi
    • Organizer
      15th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-2016)
    • Place of Presentation
      University of Pardubice (Pardubice), Czech Republic
    • Year and Date
      2016-08-28
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Phosphapyramidane2016

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, H. Sugasawa, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
    • Organizer
      21st International Conference on Phosphorus Chemistry (ICPC-XXI)
    • Place of Presentation
      Hotel Korston (Kazan), Russian Federation
    • Year and Date
      2016-06-05
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Structure of Phospha- and Bismapyramidanes2016

    • Author(s)
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      96th Annual Meeting of The Chemical Society of Japan
    • Place of Presentation
      Kyoto, Kyo-tanabe, Doshisha University
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Inverted Tetrahedral Geometry at the Main Group Elements: Pyramidanes and Propellanes.2016

    • Author(s)
      V. Ya. Lee
    • Organizer
      IInd Winter School on Organic Chemistry (WSOC-2016)
    • Place of Presentation
      Russia, Krasnovidovo, Moscow State University
    • Year and Date
      2016-01-16
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] Towards the Silicon and Germanium Versions of Metathesis: Making M=C (M = Si, Ge) Bonds2015

    • Author(s)
      V. Ya. Lee
    • Organizer
      Invited Seminar at the Okinawa Institute of Science and Technology (OIST)
    • Place of Presentation
      Japan, Okinawa, Onna, Okinawa Institute of Science and Technology
    • Year and Date
      2015-12-11
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] Cationic Pyramidanes2015

    • Author(s)
      H. Sugasawa, Y. Ito, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      The 42nd Symposium on Main Group Element Chemistry
    • Place of Presentation
      Aichi, Nagoya, Nagoya University
    • Year and Date
      2015-12-03
    • Related Report
      2015 Research-status Report
  • [Presentation] Synthesis and Structure of Cationic Pyramidanes2015

    • Author(s)
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      19th Silicon Symposium of Japan
    • Place of Presentation
      Shiga, Moriyama, Laforet Biwako
    • Year and Date
      2015-10-23
    • Related Report
      2015 Research-status Report
  • [Presentation] Cationic Phosphapyramidane: Synthesis, Structure, and Reactivity2015

    • Author(s)
      H. Sugasawa, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin
    • Organizer
      26th Symposium on Physical Organic Chemistry
    • Place of Presentation
      Ehime, Matsuyama, Ehime University & Matsuyama University
    • Year and Date
      2015-09-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Raman Study of Organometallics of a Novel Class Pyramidanes E[C4(SiMe3)4], E = Ge, Sn, Pb2015

    • Author(s)
      L. A. Leites, R. R. Aysin, S. S. Bukalov, V. Ya. Lee, H. Sugasawa, A. Sekiguchi
    • Organizer
      International Conference “Organometallic and Coordination Chemistry: Achievements and Challenges”
    • Place of Presentation
      Russia, Nizhny Novgorod, University
    • Year and Date
      2015-09-18
    • Related Report
      2015 Research-status Report
  • [Presentation] Pyramidanes: the Covalent Form of an Ionic Compound.2015

    • Author(s)
      V. Ya. Lee, O. A. Gapurenko, Y. Ito, T. Meguro, H. Sugasawa, A. Sekiguchi, R. M. Minyaev, V. I. Minkin, H. Gornitzka, R. Herber
    • Organizer
      14th International Symposium on Inorganic Ring Systems (IRIS-14)
    • Place of Presentation
      Germany, Regensburg, University of Regensburg
    • Year and Date
      2015-07-26
    • Related Report
      2015 Research-status Report
  • [Presentation] Group 14 Element Pyramidanes: Theoretical Studies.2015

    • Author(s)
      O. A. Gapurenko, V. Ya. Lee, R. M. Minyaev, V. I. Minkin, Y. Ito, T. Meguro, H. Sugasawa, A. Sekiguchi
    • Organizer
      14th International Symposium on Inorganic Ring Systems (IRIS-14)
    • Place of Presentation
      Germany, Regensburg, University of Regensburg
    • Year and Date
      2015-07-26
    • Related Report
      2015 Research-status Report
  • [Presentation] Towards the Novel Route for the Si=C Double Bond Formation: Silicon Version of the Metathesis Process2015

    • Author(s)
      V. Ya. Lee
    • Organizer
      XIIIth Andrianov Conference “Organosilicon Compounds: Synthesis, Properties, Applications”
    • Place of Presentation
      Russia, Moscow, Institute of Organoelement Compounds
    • Year and Date
      2015-06-28
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] Silicon-Containing Pyramidanes2015

    • Author(s)
      O. A. Gapurenko, V. Ya. Lee, T. Meguro, R. M. Minyaev, V. I. Minkin, A. Sekiguchi
    • Organizer
      XIIIth Andrianov Conference “Organosilicon Compounds: Synthesis, Properties, Applications”
    • Place of Presentation
      Russia, Moscow, Institute of Organoelement Compounds
    • Year and Date
      2015-06-28
    • Related Report
      2015 Research-status Report
  • [Book] Organosilicon Compounds, Volume 1: Theory and Experiment (Synthesis)2017

    • Author(s)
      V. Ya. Lee
    • Total Pages
      734
    • Publisher
      Elsevier/Academic Press
    • ISBN
      0128019816
    • Related Report
      2017 Annual Research Report
  • [Book] Organosilicon Compounds, Volume 2: Experiment (Physico-Chemical Studies) and Applications2017

    • Author(s)
      V. Ya. Lee
    • Total Pages
      397
    • Publisher
      Elsevier/Academic Press
    • ISBN
      0128142138
    • Related Report
      2017 Annual Research Report
  • [Book] Organic Redox Systems: Synthesis, Properties, and Applications2016

    • Author(s)
      V. Ya. Lee, A. Sekiguchi
    • Total Pages
      616
    • Publisher
      Wiley
    • Related Report
      2016 Research-status Report
  • [Book] Organic Redox Systems: Synthesis, Properties, and Applications2016

    • Author(s)
      Tohru Nishinaga, V. Ya. Lee, A. Sekiguchi et. al.
    • Total Pages
      616
    • Publisher
      Wiley
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2022-02-16  

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