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PYRAMIDANES: NOVEL ORGANIC CLUSTERS

Research Project

Project/Area Number 21K05017
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
Research InstitutionUniversity of Tsukuba

Principal Investigator

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

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2023: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2022: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2021: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywordscluster / calculations / cyclobutadiene dianion / germanium / group 14 element / organolithium compounds / pyramidane / X-ray diffraction / silicon / X-ray crystallography / germole / Frustrated Lewis Pair / Cluster / Inverted carbon atom / Pyramidane / Small molecules
Outline of Research at the Start

In this research, we are planning to prepare first representatives of a new highly attractive class of organic compounds, pyramidanes C[C4R4], that have never been synthesized before. Such novel cluster compounds are of particular importance from both fundamental and applied points of view.

Outline of Final Research Achievements

We comprehensively investigated reactivity of the novel Main Group element polyhedral clusters, pyramidanes, towards a range of nucleophilic reagents, first of all, organolithium reagents. In these reactions, pyramidanes revealed an unprecedented electrophilic behavior, which allowed for the smooth approach to a variety of organometallic derivatives featuring E-Li (E = Ge, Sn) bonding. The latter compounds can be readily functionalized with appropriate electrophiles, forming a series of synthetically useful metallole derivatives.
Based on this (and previous) research, we made general conclusions regarding the reaction pathways and mechanisms in the reaction of the cyclobutadiene dianion derivative with the Main Group element halides.

Academic Significance and Societal Importance of the Research Achievements

The developed strategy allows for a synthetic approach towards organometallic compounds featuring E-Li bond (E = Ge, Sn), from which a variety of germole derivatives can be prepared. The latter compounds are important as prospective ligands for transition metal complexes for advanced materials.

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • Research Products

    (33 results)

All 2024 2023 2022 2021

All Journal Article (15 results) (of which Int'l Joint Research: 15 results,  Peer Reviewed: 15 results,  Open Access: 1 results) Presentation (14 results) (of which Int'l Joint Research: 8 results,  Invited: 3 results) Book (4 results)

  • [Journal Article] Heavy Tetrel Clusters Based on the Bicyclobutane Framework: <i>Bicyclo[1.1.0]butanes</i>, <i>[1.1.1]Propellanes</i>, and <i>Tricyclo[2.1.0.0<sup>2,5</sup>]pentanes</i>2024

    • Author(s)
      Lee Vladimir Ya.、Gapurenko Olga A.
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 19 Issue: 1

    • DOI

      10.1002/asia.202300903

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study2024

    • Author(s)
      Matsui Toru、Fujiwara Jun、Fukaya Norihisa、Lee Vladimir Ya.
    • Journal Title

      Mendeleev Communications

      Volume: 34 Issue: 1 Pages: 34-38

    • DOI

      10.1016/j.mencom.2024.01.011

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Novel Highly Effective Second-generation Grubbs Pre-catalyst for the Ring-closing Metathesis2023

    • Author(s)
      M. Yamane, Y. Seo, W. S. Putro, M. Faried, V. Ya. Lee, T. Mizusaki, Y. Takagi, K. Matsumoto, J.-C. Choi, N. Fukaya
    • Journal Title

      Journal of the Japan Petroleum Institute

      Volume: 66 Issue: 1 Pages: 23-26

    • DOI

      10.1627/jpi.66.23

    • ISSN
      1346-8804, 1349-273X
    • Year and Date
      2023-01-01
    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Hybrid Bicyclo[1.1.0]butanes [(R4Si3)CH2] and [(R4Si2Ge)CH2] (R = SiMet-Bu2): Synthesis and Thermal Isomerization to Alkyl-Substituted Cyclopropenes [R3Si3]CH2R and [R3Si2Ge]CH2R.2023

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

      Organometallics

      Volume: 42 Issue: 18 Pages: 2514-2521

    • DOI

      10.1021/acs.organomet.2c00599

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Novel second-generation Hoveyda-Grubbs metathesis pre-catalyst2023

    • Author(s)
      M. Yamane, Y. Seo, W. S. Putro, V. Ya. Lee, T. Mizusaki, Y. Takagi, K. Matsumoto, J.-C. Choi, N. Fukaya
    • Journal Title

      Russ. Chem. Bull., Int. Ed.

      Volume: 72 Pages: 2762-2764

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Pyramidanes: newcomers to the anti-van’t Hoff-Le Bel family2023

    • Author(s)
      Lee Vladimir Ya.、Gapurenko Olga A.
    • Journal Title

      Chemical Communications

      Volume: 59 Issue: 67 Pages: 10067-10086

    • DOI

      10.1039/d3cc02757k

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Organogermanium Analogues of Alkenes, Alkynes, 1,3-Dienes, Allenes, and Vinylidenes.2023

    • Author(s)
      V. Ya. Lee
    • Journal Title

      Molecules

      Volume: 28 Issue: 4 Pages: 1558-1558

    • DOI

      10.3390/molecules28041558

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Group 4 metal silylidenes and germylidenes: towards the silicon and germanium variations of olefin metathesis.2023

    • Author(s)
      V. Ya. Lee
    • Journal Title

      Mendeleev Communications

      Volume: 33 Issue: 2 Pages: 145-152

    • DOI

      10.1016/j.mencom.2023.02.001

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Schrock‐Type Silylidenes and Germylidenes Found Among the Silylene and Germylene Complexes of the Early and Mid‐Transition Metals.2022

    • Author(s)
      V. Ya. Lee
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2022 Issue: 23

    • DOI

      10.1002/ejic.202200175

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 1-Chloroalumole2022

    • Author(s)
      Lee Vladimir Ya.、Sugasawa Haruka、Gapurenko Olga A.、Minyaev Ruslan M.、Minkin Vladimir I.、Gornitzka Heinz、Sekiguchi Akira
    • Journal Title

      Organometallics

      Volume: 41 Issue: 4 Pages: 467-471

    • DOI

      10.1021/acs.organomet.1c00702

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Phosphatetrasilatricyclo[2.1.0.02,5]pentane2022

    • Author(s)
      Ya. Lee Vladimir、Meguro Takahiko、Gapurenko Olga A.、Minyaev Ruslan M.、Minkin Vladimir I.、Gornitzka Heinz、Sekiguchi Akira
    • Journal Title

      Mendeleev Communications

      Volume: 32 Issue: 1 Pages: 33-34

    • DOI

      10.1016/j.mencom.2022.01.009

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ferrocene‐Based Phosphenium Ion with Intramolecular Phosphine Coordination2021

    • Author(s)
      Zhang Tianqing、Lee Vladimir Ya.、Morisako Shogo、Aoyagi Shinobu、Sasamori Takahiro
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2021 Issue: 38 Pages: 3988-3991

    • DOI

      10.1002/ejic.202100615

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] [Pd(4-RSi-IPr)(allyl)Cl]/KCO/EtOH: A highly effective catalytic system for the Suzuki-Miyaura cross-coupling reaction2021

    • Author(s)
      Seo Yuto、Putro Wahyu S.、Faried Miftah、Lee Vladimir Ya.、Mizusaki Tomoteru、Takagi Yukio、Choe Yoong-Kee、Matsumoto Kazuhiro、Choi Jun-Chul、Fukaya Norihisa
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 954-955 Pages: 122096-122096

    • DOI

      10.1016/j.jorganchem.2021.122096

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Si3S-Bicyclo[1.1.0]butane vs. Si3S-cyclobutene: an isomeric interplay2021

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

      Russian Chemical Bulletin, International Edition

      Volume: 70 Pages: 2233-2235

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] From SiO2 to Alkoxysilanes for the Synthesis of Useful Chemicals2021

    • Author(s)
      Putro Wahyu S.、Lee Vladimir Ya.、Sato Kazuhiko、Choi Jun-Chul、Fukaya Norihisa
    • Journal Title

      ACS Omega

      Volume: 6 Issue: 51 Pages: 35186-35195

    • DOI

      10.1021/acsomega.1c05138

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Reactivity of Germapyramidane Towards Organolithium Reagents2024

    • Author(s)
      J. Wang, V. Ya. Lee, K. Takeuchi, N. Fukaya, T. Sasamori
    • Organizer
      104th Annual Meeting of The Chemical Society of Japan, Japan, Funabashi, Nihon University, 18-21 March 2024, E1111-4pm-07.
    • Related Report
      2023 Annual Research Report
  • [Presentation] Group 4 Metal Silylidenes and Germylidenes2023

    • Author(s)
      V. Ya. Lee, S. Aoki, T. Yokoyama, R. Sakai, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev
    • Organizer
      6th EuChemS Inorfanic Chemistry Conference (EICC-6), Austria, Vienna, September 3-7, 2023, O-52.
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Reactivity of Germapyramidane2023

    • Author(s)
      J. Wang, V. Ya. Lee, T. Sasamori
    • Organizer
      103rd Annual Meeting of The Chemical Society of Japan, Japan, Noda, Tokyo
    • Related Report
      2022 Research-status Report
  • [Presentation] Pyramidanes: The Covalent Form of the Ionic Compounds2022

    • Author(s)
      V. Ya. Lee
    • Organizer
      International Conference on Noncovalent Interactions (ICNI-2), Strasbourg, France
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Increasing Complexity of the Main Group Element Clusters: From Bicyclic Bicyclobutanes to Tricyclic Propellanes to Tetracyclic Pyramidanes2022

    • Author(s)
      V. Ya. Lee
    • Organizer
      16th International Symposium on Inorganic Ring Systems (IRIS-16), Graz, Austria
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of a Phosphine-Stabilized Phosphenium Ion Incorporated into a [2]Ferrocenophane Framework2022

    • Author(s)
      T. Zhang, V. Ya. Lee, S. Aoyagi, T. Sasamori
    • Organizer
      16th International Symposium on Inorganic Ring Systems (IRIS-16), Graz, Austria
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Schrock-Type Silylidenes and Germylidenes2022

    • Author(s)
      V. Ya. Lee, S. Aoki, T. Yokoyama, S. Horiguchi, R. Sakai, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev
    • Organizer
      44th International Conference on Coordination Chemistry (ICCC-44), Rimini, Italy
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Catalytic Performance Evaluation of Ru Complexes with Silyl-Substituted N-Heterocyclic Carbene Ligands2022

    • Author(s)
      M. Yamane, Y. Seo, W. S. Putro, M. Faried, V. Ya. Lee, T. Mizusaki, Y. Takagi, K. Matsumoto, J.-C. Choi, N. Fukaya
    • Organizer
      The Japan Petroleum Institute Conference, Tokyo, Japan
    • Related Report
      2022 Research-status Report
  • [Presentation] [Pd(4-R3Si-IPr)(allyl)Cl]: A Highly Effective Catalytic System for the C-N and C-C couplings2022

    • Author(s)
      M. Faried, Y. Seo, W. S. Putro, V. Ya. Lee, T. Mizusaki, Y. Takagi, Y.-K. Choe, K. Matsumoto, J.-C. Choi, N. Fukaya
    • Organizer
      The 9th Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT9), Fukuoka, Japan
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Isolation of Phosphine-Stabilized Phosphenium Complexes with a [2]Ferrocenophane Framework2022

    • Author(s)
      T. Zhang, V. Ya. Lee, S. Aoyagi, T. Sasamori
    • Organizer
      102nd Annual Meeting of The Chemical Society of Japan
    • Related Report
      2021 Research-status Report
  • [Presentation] Synthesis of a Stable Phosphine-Stabilized Phosphenium Complex Based on the Sterically Demanding Ferrocenyl Frameworks2021

    • Author(s)
      T. Zhang, V. Ya. Lee, S. Aoyagi, T. Sasamori
    • Organizer
      23rd International Conference on Phosphorus Chemistry (ICPC-23)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Aromatic Compounds of the Heavier Group 13-15 Elements2021

    • Author(s)
      V. Ya. Lee
    • Organizer
      PACIFICHEM-2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Stable Ferrocene-Based Phosphenium Ion with Intramolecular Phosphine Coordination2021

    • Author(s)
      T. Zhang, V. Ya. Lee, S. Aoyagi, T. Sasamori
    • Organizer
      31st Symposium on Physical Organic Chemistry
    • Related Report
      2021 Research-status Report
  • [Presentation] Ferrocene-Based Phosphenium Ion with Intramolecular Phosphine Coordination2021

    • Author(s)
      T. Zhang, V. Ya. Lee, T. Sasamori
    • Organizer
      48th Symposium on Main Group Element Chemistry
    • Related Report
      2021 Research-status Report
  • [Book] Organogermanium Compounds: Theory, Experiment, and Applications (2 Volumes)2023

    • Author(s)
      V. Ya. Lee (Editor)
    • Total Pages
      896
    • Publisher
      Wiley
    • ISBN
      9781119613435
    • Related Report
      2023 Annual Research Report 2022 Research-status Report
  • [Book] Chapter 10 "Multiple Bonds to Germanium", in "Organogermanium Compounds: Theory, Experiment, and Applications" (Ed.: V. Ya. Lee)2023

    • Author(s)
      V. Ya. Lee
    • Total Pages
      40
    • Publisher
      Wiley
    • ISBN
      9781119613435
    • Related Report
      2023 Annual Research Report
  • [Book] Comprehensive Inorganic Chemistry III (Eds. J. Reedijk, K. Poeppelmeier), Vol. 1, Chapter "Low-Coordinate Compounds of Heavier Group 14-16 Elements"2023

    • Author(s)
      T. Sasamori, V. Ya. Lee, N. Nagahora, S. Morisako
    • Total Pages
      73
    • Publisher
      Elsevier
    • ISBN
      9780128231449
    • Related Report
      2022 Research-status Report
  • [Book] Organogermanium Compounds: Theory, Experiment, and Applications, Chapter 10 "Multiple Bonds to Germanium"2023

    • Author(s)
      V. Ya. Lee
    • Total Pages
      41
    • Publisher
      Wiley
    • ISBN
      9781119613435
    • Related Report
      2022 Research-status Report

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Published: 2021-04-28   Modified: 2025-01-30  

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