σ-Aromaticity in hexa-group 16 atom-substituted benzene dications: a theoretical study.
σ-Aromaticity in hexa-group 16 atom-substituted benzene dications: a theoretical study.
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六族 16 原子取代的苯二酮中的 σ-芳香性：理论研究。
DOI：
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发表时间：
2014
影响因子：
3.6
通讯作者：
K. Morokuma
中科院分区：
文献类型：
--
作者：
Miho Hatanaka;Masaichi Saito;M. Fujita;K. Morokuma
据报道，C6I6(2+) 具有 σ 芳香族特征，因为去除碘上的两个 σ 反键电子可满足 I6(2+) 和 C6 部分的 Hückel (4n+2) 规则。为了寻找具有相似特征的分子，通过使用核无关化学位移 (NICS) 检查六族 16 原子取代的苯二离子 C6(ChH)6(2+) (Ch = S、Se、Te) 及其衍生物的芳香特征。对于这些双阳离子，其中 C6I6(2+) 中的碘被第 16 族原子取代，当位于第 16 族原子上的 σ 反键轨道未被占据时，会发现比苯更大的负 NICS 值。为了澄清大的负 NICS 值的来源，它们被分解为单独的分子轨道。研究表明，C6 上的 π 键合轨道和 Se6 或 Te6 上的 σ 键合轨道都会导致 NICS 值为负值，表明这些双离合的芳香性具有显着的 σ 特征以及 π 特征。还讨论了第 14 族和第 15 族原子取代的苯二离子的芳香性。
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.
影响因子：
4.3
作者：
Molski, Matthias J.;Mollenhauer, Doreen;Seppelt, Konrad
通讯作者：
Seppelt, Konrad