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2014 Fiscal Year Annual Research Report

シリレンおよびゲルミレンを配位子とするシュロック型遷移金属錯体の合成と構造

Research Project

Project/Area Number 24550038
Research InstitutionUniversity of Tsukuba

Principal Investigator

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

Project Period (FY) 2012-04-01 – 2015-03-31
Keywordscycloaddition / germylene / metathesis / Schrock complex / silylene
Outline of Annual Research Achievements

Metathesis of unsaturated hydrocarbons (alkenes, alkynes) as well as its numerous variations, such as cross-metathesis, ring-closing metathesis, ring-opening metathesis, ring-opening-metathesis polymerization, etc., is among the most technologically useful and ecologically friendly alkene transformations. The silicon and germanium variations of the metathesis process represent a totally new and very promising route for the synthesis of the highly reactive multiply-bonded organosilicon and organogermanium compounds, which may serve as the precursors for the advanced materials of the new generation. However, despite such evident interest, to date there were no reports about any success in the field of silicon and germanium metathesis. In this project we developed first examples of the Schrock-type alkylidene complexes of silicon and germanium, namely, silylidenes and germylidenes of the early transition metals. Unprecedented examples of the stable silylene and germylene complexes of the group 4 metals were prepared and isolated in high yields, structurally characterized and computationally studied. All experimental and computational data firmly support classification of such complexes as Schrock-type silylidenes and germylidenes. The above-described Schrock complexes readily react with a variety of unsaturated substratesforming the corresponding [2 + 2] cycloadducts, whose particular structures were comprehensively studied both experimentally and computationally. The cycloreversion of the newly synthesized metallacyclobutanes and metallacyclobutenes will be studied.

  • Research Products

    (14 results)

All 2015 2014 Other

All Journal Article (5 results) (of which Peer Reviewed: 5 results) Presentation (7 results) (of which Invited: 2 results) Book (1 results) Remarks (1 results)

  • [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 Pages: in press

    • 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 Pages: in press

    • DOI

      10.1002/anie.201500731

    • Peer Reviewed
  • [Journal Article] 1,1-Dilithiosilanes, 1,1-Dilithiogermanes and 1,1-Dilithiostannanes (and Related Compounds): Organometallic Reagents of the New Generation.2015

    • Author(s)
      Vladimir Ya. Lee, Akira Sekiguchi
    • Journal Title

      Mend. Commun.

      Volume: 25 Pages: in press

    • Peer Reviewed
  • [Journal Article] Tetrakis(di-tert-butylmethylsilyl)digermene: Synthesis, Structure, Electrochemical Properties, and Reactivity.2014

    • Author(s)
      Vladimir Ya. Lee, Kiera McNeice, Yuki Ito, Akira Sekiguchi, Natalie Geinik, James Y. Becker
    • Journal Title

      Heteroatom Chemistry

      Volume: 25 Pages: 313-319

    • DOI

      10.1002/hc.21165

    • Peer Reviewed
  • [Journal Article] Reactivity of a Spirobis(pentagerma[1.1.1]propellane).2014

    • Author(s)
      Vladimir Ya. Lee, Yuki Ito, Akira Sekiguchi
    • Journal Title

      Main Group Metal Chemistry

      Volume: 37 Pages: 149-151

    • DOI

      10.1515/mgmc-2014-0017

    • Peer Reviewed
  • [Presentation] Cationic Pyramidanes with the Apical Heavier Group 15 Element.2015

    • Author(s)
      H. Sugasawa, Y. Ito, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin,
    • Organizer
      95th Annual Meeting of The Chemical Society of Japan
    • Place of Presentation
      日本大学,船橋
    • Year and Date
      2015-03-26 – 2015-03-29
  • [Presentation] In search for Hybrid Pyramidanes with the Si4-Base and Heaviest Group 14/Group 15 Element at the Apex.2015

    • Author(s)
      T. Meguro, V. Ya. Lee, A. Sekiguchi, O. A. Gapurenko, R. M. Minyaev, V. I. Minkin,
    • Organizer
      95th Annual Meeting of The Chemical Society of Japan
    • Place of Presentation
      日本大学,船橋
    • Year and Date
      2015-03-26 – 2015-03-29
  • [Presentation] Bis(stibahousene).2015

    • Author(s)
      O. A. Gapurenko, V. I. Minkin, R. M. Minyaev, V. Ya. Lee, Y. Ito, A. Sekiguchi,
    • Organizer
      XII International Workshop on Magnetic Resonance (Spectroscopy, Tomography and Ecology)
    • Place of Presentation
      Rostov-on-Don, Russia
    • Year and Date
      2015-03-02 – 2015-03-07
  • [Presentation] Toward the Silicon and Germanium Versions of Metathesis.2014

    • Author(s)
      V. Ya. Lee
    • Organizer
      XIth International Conference on Spectroscopy of Coordination Compounds
    • Place of Presentation
      Tuapse, Russia
    • Year and Date
      2014-09-21 – 2014-09-27
    • Invited
  • [Presentation] Pyramidanes: the Covalent Form of an Ionic Compound.2014

    • Author(s)
      V. Ya. Lee, Y. Ito, T. Meguro, A. Sekiguchi, H. Gornitzka, O. A. Gapurenko, V. I. Minkin, R. M. Minyaev,
    • Organizer
      17th International Symposium on Silicon Chemistry (ISOS XVII)
    • Place of Presentation
      Berlin, Germany
    • Year and Date
      2014-08-03 – 2014-08-08
    • Invited
  • [Presentation] Toward the Silicon/Germanium Versions of Metathesis.2014

    • Author(s)
      V. Ya. Lee, S. Aoki, T. Yokoyama, R. Sakai, A. Sekiguchi.
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC 2014)
    • Place of Presentation
      Sapporo
    • Year and Date
      2014-07-13 – 2014-07-18
  • [Presentation] Pyramidanes: Insights into Non-Classical Bonding Nature.2014

    • Author(s)
      Y. Ito, T. Meguro, V. Ya. Lee, A. Sekiguchi,
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC 2014)
    • Place of Presentation
      Sapporo
    • Year and Date
      2014-07-13 – 2014-07-18
  • [Book] Heavier Group 14 Element Redox Systems.2015

    • Author(s)
      Vladimir Ya. Lee, Akira Sekiguchi
    • Total Pages
      in press
    • Publisher
      Wiley, Hoboken
  • [Remarks] 関口研究室ホームページ

    • URL

      http://www.chem.tsukuba.ac.jp/sekiguch/

URL: 

Published: 2016-06-01  

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