σ-aromaticity in hexa-group 16 atom-substituted benzene dications: A theoretical study

Miho Hatanaka, Masaichi Saito, Masahiro Fujita, Keiji Morokuma

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

C6I62+ has been reported to have a σ-aromatic character since removal of two σ anti-bonding electrons localized on iodines results in fulfilling Hückel (4n+2) rules for I 62+ as well as C6 parts. To search for molecules possessing similar character, hexa-group 16 atom-substituted benzene dications C6(ChH)62+ (Ch = S, Se, Te) and their derivatives are examined for aromatic character by using nucleus-independent chemical shift (NICS). For these dications, in which iodines in C 6I62+ are replaced by group 16 atoms, negative NICS values larger in magnitude than for benzene are found when a σ anti-bonding orbital localized on group 16 atoms is unoccupied. To clarify the origin of large negative NICS values, they are decomposed into individual molecular orbitals. It has been shown that both π bonding orbitals on C 6 and σ bonding orbitals on Se6 or Te6 contribute to the negative NICS values, indicating that the aromaticity of these dications have a substantial σ character as well as π characters. Aromaticity of group 14 and 15 atom-substituted benzene dications is also discussed.

Original languageEnglish
Pages (from-to)2640-2646
Number of pages7
JournalJournal of Organic Chemistry
Volume79
Issue number6
DOIs
Publication statusPublished - 2014 Mar 21
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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