Binuclear Sandwiches of the Main Group Elements

• Project/Area Number: 18K05137
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 34010:Inorganic/coordination chemistry-related
• Research Institution: University 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
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2018: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: cluster / cyclobutadiene dianion / housene / pyramidane / bis(housene) / group 14 element / group 15 element / multidecker sandwich / Cluster / Group 15 element / Binuclear sandwich / Pyramidane / Bis(housene) / Cyclobutadiene dianion / NMR spectroscopy / X-ray crystallography / binuclear sandwich / group 13 element / bis(pyramidane) / silicon / germanium / structure

Outline of Final Research Achievements

The multidecker polynuclear sandwiches with the main group elements represent a novel class of polyhedral clusters which recently attracted a great interest due to their potential use in photonic devices, optical data storage and data transmission. However, none of these complexes were isolated and characterized. In the current project, we developed a new synthetic strategy towards such sandwich clusters based on the reaction of the cyclobutadiene dianions with the main group element halides forming a wide range of housenes or pyramidanes. By dimerization of housenes we succeeded in the preparation of the first representatives of bis(housenes) which exhibited very unusual structural and reactivity features.

Academic Significance and Societal Importance of the Research Achievements

We developed a synthetic route to unprecedented class of the main group clusters, bis(housenes) and their derivatives. Based on the magnetic and transport properties of these complexes, they can be used in molecular spintronics for quantum computing and high-performance nonlinear optics materials.

Research Products

• [Journal Article] Titanium Germylidenes (2021)
  • Author(s): Lee Vladimir Ya.、Sakai Ryo、Takanashi Kazunori、Gapurenko Olga A.、Minyaev Ruslan M.、Gornitzka Heinz、Sekiguchi Akira
  • Journal Title: Angewandte Chemie International Edition Volume: 60 Issue: 8 Pages: 3951-3955
  • DOI: 10.1002/anie.202015704
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] From a (Silatrigerma)cyclobutenylium Ion to a (Silatrigerma)cyclobutenyl Radical and Back (2020)
  • Author(s): Lee Vladimir Ya.、Ito Yuki、Gapurenko Olga A.、Minyaev Ruslan M.、Gornitzka Heinz、Sekiguchi Akira
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 38 Pages: 16455-16460
  • DOI: 10.1021/jacs.0c08052
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Sustainable Catalytic Synthesis of Diethyl Carbonate (2020)
  • Author(s): Putro Wahyu S.、Ikeda Akira、Shigeyasu Shinji、Hamura Satoshi、Matsumoto Seiji、Lee Vladimir Ya.、Choi Jun‐Chul、Fukaya Norihisa
  • Journal Title: ChemSusChem Volume: 14 Issue: 3 Pages: 842-846
  • DOI: 10.1002/cssc.202002471
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 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)
  • Author(s): R. R. Aysin, S. S. Bukalov, L. A. Leites, V. Ya. Lee, A. Sekiguchi
  • Journal Title: J. Organomet. Chem. Volume: 892 Pages: 18-23
  • DOI: 10.1016/j.jorganchem.2019.04.014
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Theoretical Prediction for Synthetic Realization: Pyramidal Systems for Synthetic Realization ClE[E4R4] (E = B-Ga, E = C-Ge, R = SiMe3, SiMetBu2): A DFT Study (2019)
  • Author(s): O. A. Gapurenko, V. Ya. Lee, R. M. Minyaev, V. I. Minkin
  • Journal Title: Heteroatom Chem. Volume: - Pages: 3659287-3659287
  • DOI: 10.1155/2019/3659287
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] [2 + 2] Cycloadduct of Titanium Silylidene and Benzonitrile (2019)
  • Author(s): V. Ya. Lee, S. Horiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin, H. Gornitzka, A. Sekiguchi
  • Journal Title: Eur. J. Inorg. Chem. Volume: - Issue: 39-40 Pages: 4224-4227
  • DOI: 10.1002/ejic.201900601
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Tricoordinate Silicon Cations (Silylium Ions) (invited) (2019)
  • Author(s): V. Ya. Lee
  • Journal Title: Russ. Chem. Rev. Volume: 88 Issue: 4 Pages: 351-369
  • DOI: 10.1070/rcr4868
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] [Pd(4-R3Si-IPr)(allyl)Cl], a Family of Silyl-Substituted Pd－NHC Complexes: Catalytic Systems for the Buchwald－Hartwig Amination (2019)
  • 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 Issue: 2 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－IPr (2019)
  • 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 Issue: 2 Pages: 2902-2906
  • DOI: 10.1021/acsomega.8b03429
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] From Borapyramidane to Borole Dianion (2018)
  • 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 Issue: 19 Pages: 6053-6056
  • DOI: 10.1021/jacs.8b03473
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Arsagermene, a compound with an As=Ge double bond (2018)
  • Author(s): V. Ya. Lee,* M. Kawai, O. A. Gapurenko, V. I. Minkin, H. Gornitzka, A. Sekiguchi
  • Journal Title: Chem. Commun. Volume: 54 Issue: 78 Pages: 10947-10949
  • DOI: 10.1039/c8cc05630g
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Schrock-Type Silylidenes and Germylidenes (2019)
  • Author(s): V. Ya. Lee
  • Organizer: 2nd International Conference of Hyper- and Hypocoordinated Compounds of the Group 14 Elements, France, Rennes, June 19-21
  • Invited
• [Presentation] Pyramidane: The Smallest Member of the Fenestranes Family (2019)
  • Author(s): V. Ya. Lee, O. A. Gapurenko, A. Sekiguchi, R. M. Minyaev, V. I. Minkin
  • Organizer: 5th EuChemS Inorganic Chemistry Conference (EICC-5), Russia, Moscow, June 24-28
  • Invited
• [Presentation] Cyclobutadiene Complexes of the s-, p-, and d-Block Elements (2019)
  • Author(s): V. Ya. Lee
  • Organizer: 13th International Conference on Heteroatom Chemistry (ICHAC 2019), Czech Republic, Prague, June 30-July 5
  • Invited
• [Presentation] Group 4 Metal Germylidenes (and Related Complexes) (2019)
  • Author(s): V. Ya. Lee, R. Sakai, T. Yokoyama, S. Aoki, K. Takanashi, A. Sekiguchi
  • Organizer: 16th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (GTL-2019), Japan, Saitama, September 1-6
• [Presentation] Alkene Metathesis: Silicon and Germanium Versions (2019)
  • Author(s): V. Ya. Lee
  • Organizer: XXIth Mendeleev Congress on General and Applied Chemistry, Saint-Petersburg, Russia, September 9-13
  • Invited
• [Presentation] Pyramidanes (2019)
  • Author(s): V. Ya. Lee
  • Organizer: Visiting Professor at the Graz University of Technology, Graz, Austria, 18-28 October
  • Invited
• [Presentation] Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes (2019)
  • Author(s): Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, K. Matsumoto, J.-C. Choi, N. Fukaya
  • Organizer: 8th JACI/GSC Symposium 2019(Japan Association for Chemical Innovation/Green and Sustainable Chemistry), Tokyo, Tokyo International Forum, 24-25 June
• [Presentation] Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes (2019)
  • Author(s): Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, K. Matsumoto, J.-C. Choi, N. Fukaya
  • Organizer: 66th Symposium on Organometallic Chemistry, Tokyo, Tokyo Metropolitan University, 14-16 September
• [Presentation] Catalytic Performance of Silyl Group-Substituted N-Heterocyclic Carbene Complexes (2019)
  • Author(s): Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, Y.-K. Choe, K. Matsumoto, J.-C. Choi, N. Fukaya
  • Organizer: 100th Annual Meeting of The Chemical Society of Japan, Noda, Tokyo University of Science, 22-25 March
• [Presentation] Computational Chemical Verification of Activation of [R3Si-IPr]Pd Catalyst Precursor in Suzuki-Miyaura Cross-Coupling Reaction (2019)
  • Author(s): J. Fujiwara, Y. Ozaki, V. Ya. Lee, T. Matsui, K. Morihashi
  • Organizer: 100th Annual Meeting of The Chemical Society of Japan, Noda, Tokyo University of Science, 22-25 March
• [Presentation] Pyramidanes: Study of the Electronic Structures of Pyramidal Compounds and Their NMR Properties (2019)
  • 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 Elements (2018)
  • 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 Pyramidanes (2018)
  • 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 Clusters (2018)
  • 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 Compounds (2018)
  • 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] Pyramidanes (2018)
  • 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 Complexes (2018)
  • 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