Crystal and Electronic Structures of [5]Radialene Substituted with Quintuple 1,3‐Dithiol‐2‐ylidenes and Its Oxidative Species

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  • Masafumi Ueda
    Department of Applied Chemistry Graduate School of Engineering Ehime University Matsuyama, Ehime 790-8577 Japan
  • Takashi Shirahata
    Department of Applied Chemistry Graduate School of Engineering Ehime University Matsuyama, Ehime 790-8577 Japan
  • Yohji Misaki
    Department of Applied Chemistry Graduate School of Engineering Ehime University Matsuyama, Ehime 790-8577 Japan

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<jats:title>Abstract</jats:title><jats:p>X‐ray structure analysis of the [5]radialene with quintuple 1,3‐benzodithiol‐2‐ylidenes (<jats:bold>4</jats:bold>) and its tetracation salt, <jats:bold>4 a</jats:bold>⋅CS<jats:sub>2</jats:sub> and (<jats:bold>4 a</jats:bold>)<jats:sup>4+</jats:sup>(ReO<jats:sub>4</jats:sub><jats:sup>–</jats:sup>)<jats:sub>4</jats:sub>(CH<jats:sub>3</jats:sub>CN), was successfully carried out. The neutral [5]radialene molecule in <jats:bold>4</jats:bold>⋅CS<jats:sub>2</jats:sub> adopted a non‐planar structure with an envelope conformation of the central five‐membered ring. In contrast, the central five‐membered ring of <jats:bold>4 a</jats:bold><jats:sup>4+</jats:sup> in (<jats:bold>4 a</jats:bold>)<jats:sup>4+</jats:sup>(ReO<jats:sub>4</jats:sub><jats:sup>−</jats:sup>)<jats:sub>4</jats:sub>(CH<jats:sub>3</jats:sub>CN) adopted a planar structure with significant contribution of an aromatic cyclopentadienide structure. An anion‐π interaction was observed between the ReO<jats:sub>4</jats:sub><jats:sup>–</jats:sup> anion and the central five‐membered ring in (<jats:bold>4 a</jats:bold>)<jats:sup>4+</jats:sup>(ReO<jats:sub>4</jats:sub><jats:sup>–</jats:sup>)<jats:sub>4</jats:sub>(CH<jats:sub>3</jats:sub>CN). The electronic structures of <jats:bold>4 a</jats:bold> and its oxidative species (<jats:bold>4 a</jats:bold><jats:sup>2+</jats:sup> and <jats:bold>4 a</jats:bold><jats:sup>4+</jats:sup>) were estimated by density functional theory (DFT) calculations. The optimized structure of <jats:bold>4</jats:bold><jats:sup>2+</jats:sup> suggested the delocalization of a positive charges over two 1,3‐benzodithiol‐2‐ylidene units through the central five‐membered ring.</jats:p>

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