Benzodisilacyclobutadienes: 8π‐Electron Systems with an Antiaromatic Silicon Ring

  • Shintaro Ishida
    Department of Chemistry Graduate School of Science Tohoku University Aoba-ku Sendai 980–8578 Japan
  • Yoshifumi Misawa
    Department of Chemistry Graduate School of Science Tohoku University Aoba-ku Sendai 980–8578 Japan
  • Shohei Sugawara
    Department of Chemistry Graduate School of Science Tohoku University Aoba-ku Sendai 980–8578 Japan
  • Takeaki Iwamoto
    Department of Chemistry Graduate School of Science Tohoku University Aoba-ku Sendai 980–8578 Japan

書誌事項

公開日
2017-10-02
資源種別
journal article
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/anie.201707553
  • 10.1002/ange.201707553
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>Benzodisilacyclobutadienes <jats:bold>2 a</jats:bold>–<jats:bold>c</jats:bold> were isolated as blue to green crystalline solids from the reaction of stable disilyne <jats:bold>1</jats:bold> and 1,2‐dibromobenzenes in the presence of potassium graphite. In the solid state, substantial bond alternation was observed within the benzene rings of <jats:bold>2 a</jats:bold>–<jats:bold>c</jats:bold>. In hexane, <jats:bold>2 a</jats:bold>–<jats:bold>c</jats:bold> showed remarkable bathochromic shifts of the π→π* (HOMO→LUMO) absorption bands at 625–670 nm. NMR spectra and theoretical calculations indicated that the diamagnetic ring currents of the benzene rings of <jats:bold>2 a</jats:bold>–<jats:bold>c</jats:bold> are considerably reduced by contributions from the antiaromatic 1,2‐disilacyclobutadienes. In their entirety, the obtained results indicate that <jats:bold>2 a</jats:bold>–<jats:bold>c</jats:bold> represent 8π‐electron systems that contain an antiaromatic 1,2‐disilacyclobutadiene.</jats:p>

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