Gas‐Phase Characterization of Hypervalent Carbon Compounds Bearing 7‐6‐7‐Ring Skeleton: Penta‐ <i>versus</i> Tetra‐Coordinate Isomers

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  • Satoru Muramatsu
    Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University 1-3-1 Kagamiyama Higashi Hiroshima 739-8526 Japan
  • Keijiro Ohshimo
    Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba, Aramaki, Aoba-ku Sendai 980-8578 Japan
  • Yuan Shi
    Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University 1-3-1 Kagamiyama Higashi Hiroshima 739-8526 Japan
  • Motoki Kida
    Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University 1-3-1 Kagamiyama Higashi Hiroshima 739-8526 Japan
  • Rong Shang
    Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University 1-3-1 Kagamiyama Higashi Hiroshima 739-8526 Japan
  • Yohsuke Yamamoto
    Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University 1-3-1 Kagamiyama Higashi Hiroshima 739-8526 Japan
  • Fuminori Misaizu
    Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba, Aramaki, Aoba-ku Sendai 980-8578 Japan
  • Yoshiya Inokuchi
    Department of Chemistry Graduate School of Advanced Science and Engineering Hiroshima University 1-3-1 Kagamiyama Higashi Hiroshima 739-8526 Japan

抄録

<jats:title>Abstract</jats:title><jats:p>In this study, we afford explicit characterizations of the electronic and geometrical structures of recently reported hypervalent penta‐coordinate carbon compounds by using gas‐phase characterization techniques: photodissociation spectroscopy (PDS) and ion mobility‐mass spectrometry (IM–MS). In particular for a compound with moderately electron‐donating ligands, bearing <jats:italic>p</jats:italic>‐methylthiophenyl substituents, the coexistence of tetra‐ and penta‐coordinate isomers is confirmed, consistent with solution characterizations. It is in sharp contrast to the exclusive tetra‐coordinate form (with normal valence of the central carbon atom) in the single crystal. This suggests that a non‐polar environment makes the penta‐coordinate structure thermodynamically most stable. This delicate difference between the tetra‐ and penta‐coordinate structures, which depends on the environment, is a close reflection of the lower activation barrier of the S<jats:sub>N</jats:sub>2 reaction found in neutral solvent or gas‐phase reactions.</jats:p>

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