Neutral Chromium Complex with a Cr≡Si Triple Bond: Synthesis and Photoinduced H−H and Benzene C−H Bond Activation

  • Masahiro Matsuoka
    Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba Sendai Miyagi 980–8578 Japan
  • Koichi Nagata
    Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba Sendai Miyagi 980–8578 Japan
  • Ryoma Ohno
    Department of Applied Chemistry Faculty of Science and Engineering Kindai University 3-4-1 Kowakae Higashi Osaka, Osaka 577-8502 Japan
  • Tsukasa Matsuo
    Department of Applied Chemistry Faculty of Science and Engineering Kindai University 3-4-1 Kowakae Higashi Osaka, Osaka 577-8502 Japan
  • Hiromi Tobita
    Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba Sendai Miyagi 980–8578 Japan
  • Hisako Hashimoto
    Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba Sendai Miyagi 980–8578 Japan

書誌事項

公開日
2023-12-22
資源種別
journal article
権利情報
  • http://creativecommons.org/licenses/by-nc-nd/4.0/
DOI
  • 10.1002/chem.202303765
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>A neutral silylyne complex with a Cr≡Si triple bond was prepared by dehydrogenation of a chromium silylene complex with Cr−H and Si−H bonds, and was isolated as monomeric crystals, unlike dimeric forms of its tungsten and molybdenum congeners. The strong Cr(<jats:italic>δ</jats:italic>−)−Si(<jats:italic>δ</jats:italic>+) bond polarity was revealed by the reaction with MeOH and DFT calculations. The chromium silylyne complex reacted with H<jats:sub>2</jats:sub> under LED (365 nm) irradiation to reproduce the precursor silylene complex with a (H)Cr=Si(H) moiety, as a result of 1,2‐H−H addition across the Cr≡Si triple bond. Similarly, the chromium silylyne complex reacted with benzene under irradiation to afford an 1,2‐addition product with a (H)Cr=Si(Ph) moiety, via benzene C−H bond activation accompanied by Si−C bond forming.</jats:p>

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