Pyramidal Structures: New Type of Cluster Compounds

• Project/Area Number: 15K05413
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: University 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: ¥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)
• Keywords: cluster / 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.

Research Products

• [Int'l Joint Research] Southern Federal University(ロシア連邦)
• [Int'l Joint Research] Southern Federal University(ロシア連邦)
• [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
  • 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
  • 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
  • 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
  • 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
  • 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
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] [2+2] Cycloaddition of the Schrock titanium silylidene and acetylene (2016)
  • 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
  • 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
  • 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
  • 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
  • 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
  • Peer Reviewed
• [Presentation] Synthesis of Pyramidanes with the Group 13 Element at the Apex (2017)
  • 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
• [Presentation] Pyramidanes (2017)
  • 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)
  • Int'l Joint Research
• [Presentation] Pyramidanes (2017)
  • 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)
  • Int'l Joint Research
• [Presentation] Pyramidanes (2017)
  • Author(s): V. Ya. Lee
  • Organizer: Russian-French Workshop on Hyper- and Hypocoordinated Compounds of the Group 14 Elements (Moscow, Russia)
  • Int'l Joint Research / Invited
• [Presentation] Pyramidanes (2017)
  • Author(s): V. Ya. Lee
  • Organizer: VII International Symposium “Chemistry and Chemical Education” (Vladivostok, Russia)
  • Int'l Joint Research / Invited
• [Presentation] Pyramidanes (2017)
  • Author(s): V. Ya. Lee
  • Organizer: “INEOS OPEN CUP” Conference (Moscow, Russia)
  • Int'l Joint Research / Invited
• [Presentation] Invited Seminars (2017)
  • Author(s): V. Ya. Lee
  • Organizer: University of Muenster and University of Goettingen (Germany)
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of Pyramidanes with the Group 13 Element at the Apex (2017)
  • 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)
• [Presentation] Reactivity of the Cyclobutadiene Dianion Dilithium Salt Toward the Group 13 Element Halides (2016)
  • 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
• [Presentation] Anti Van’t Hoff-Le Bel Configurations as the Main Group Elements (2016)
  • 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
  • Int'l Joint Research / Invited
• [Presentation] Pyramidal Structures of Group 13 and 15 Elements with Silicon Basal Rings (2016)
  • 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
  • Int'l Joint Research
• [Presentation] Inverted Tetrahedral Geometry at the Heavier Group 14 Elements: Pyramidanes and Propellanes (2016)
  • 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
  • Int'l Joint Research / Invited
• [Presentation] Group 14 Element Pyramidanes (2016)
  • 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
  • Int'l Joint Research
• [Presentation] Phosphapyramidane (2016)
  • 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
  • Int'l Joint Research
• [Presentation] Synthesis and Structure of Phospha- and Bismapyramidanes (2016)
  • 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
• [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
  • Invited
• [Presentation] Towards the Silicon and Germanium Versions of Metathesis: Making M=C (M = Si, Ge) Bonds (2015)
  • 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
  • Invited
• [Presentation] Cationic Pyramidanes (2015)
  • 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
• [Presentation] Synthesis and Structure of Cationic Pyramidanes (2015)
  • 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
• [Presentation] Cationic Phosphapyramidane: Synthesis, Structure, and Reactivity (2015)
  • 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
• [Presentation] Raman Study of Organometallics of a Novel Class Pyramidanes E[C4(SiMe3)4], E = Ge, Sn, Pb (2015)
  • 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
• [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
• [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
• [Presentation] Towards the Novel Route for the Si=C Double Bond Formation: Silicon Version of the Metathesis Process (2015)
  • 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
  • Invited
• [Presentation] Silicon-Containing Pyramidanes (2015)
  • 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
• [Book] Organosilicon Compounds, Volume 1: Theory and Experiment (Synthesis) (2017)
  • Author(s): V. Ya. Lee
  • Total Pages: 734
  • Publisher: Elsevier/Academic Press
  • ISBN: 0128019816
• [Book] Organosilicon Compounds, Volume 2: Experiment (Physico-Chemical Studies) and Applications (2017)
  • Author(s): V. Ya. Lee
  • Total Pages: 397
  • Publisher: Elsevier/Academic Press
  • ISBN: 0128142138
• [Book] Organic Redox Systems: Synthesis, Properties, and Applications (2016)
  • Author(s): V. Ya. Lee, A. Sekiguchi
  • Total Pages: 616
  • Publisher: Wiley
• [Book] Organic Redox Systems: Synthesis, Properties, and Applications (2016)
  • Author(s): Tohru Nishinaga, V. Ya. Lee, A. Sekiguchi et. al.
  • Total Pages: 616
  • Publisher: Wiley