σ-Aromaticity in Hexa-Group 16 Atom-Substituted Benzene Dications: A Theoretical Study
Abstract
C6I6(2+) 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 I6(2+) as well as C6 parts. To search for molecules possessing similar character, hexa-group 16 atom-substituted benzene dications C6(ChH)6(2+) (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 C6I6(2+) 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 C6 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.
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The absence of EPR signals for 7 is consistent with the previous theoretical prediction that the singlet state of C6(SeH)6 2+ is more stable than the triplet state by 3 kcal mol−1.
“This experimental result is consistent with our previous theoretical prediction that a singlet state of C6(SeH)6 2 + is more stable than that of a triplet state by 3 kcal mol -133”
From Double aromaticity arising from σ- and π-rings (2018) · cites this paper as [33]
Cites
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Double aromaticity: aromaticity in orthogonal planes. The 3,5-dehydrophenyl cation.
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Double aromaticity arising from σ- and π-rings
Furukawa, S., Fujita, M., Kanatomi, Y., Minoura, M., Hatanaka, M., Morokuma, K., Ishimura, K., & Saito, M. (2018) · Communications Chemistry · doi:10.1038/s42004-018-0057-4 · Cited by 73 · see citing works
Self-citationRauhalahti, M., Taubert, S., Sundholm, D., & Liégeois, V. (2017) · Physical Chemistry Chemical Physics · doi:10.1039/c7cp00194k · Cited by 61 · see citing works
- Authors
- Hatanaka, M., Saito, M., Fujita, M., & Morokuma, K.
- Affiliations
- Fukui Institute for Fundamental Chemistry, Kyoto University (JP)
- Saitama University (JP)
- Corresponding author
- Morokuma, Keiji
- Venue
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-03-06
- Volume
- 79
- Issue
- 6
- Pages
- 2640-2646
- ISSN
- 0022-3263 (ISSN-L)
- 1520-6904
- OpenAlex
- W2317250549
- Cited by
- 14
- References
- 4
- Citations by year
- 2026: 2 · 2025: 1 · 2023: 2 · 2022: 1 · 2021: 3 · 2020: 1 · 2018: 2 · 2017: 2
- FWCI
- 0.29
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Organic Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Japan Society for the Promotion of Science (25109525)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Synthesis and Properties of Aromatic Compounds
- Physical Sciences › Chemistry › Inorganic Chemistry › Synthesis and characterization of novel inorganic/organometallic compounds
- Physical Sciences › Chemistry › Organic Chemistry › Cyclization and Aryne Chemistry
- Keywords
- sigma-aromaticity, nucleus-independent chemical shift, Hückel rule, antibonding orbitals, aromaticity
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