Homoconjugation/Homoaromaticity in Main Group Inorganic Molecules,Journal of the American Chemical Society

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Homoconjugation/Homoaromaticity in Main Group Inorganic Molecules
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-07-22 , DOI: 10.1021/ja9029285
Qin Zhang ₁ , Shiping Yue ₁ , Xin Lu ₁ , Zhongfang Chen ₁ , Rongbin Huang ₁ , Lansun Zheng ₁ , Paul von Ragué Schleyer ₁

Affiliation

Quantum chemical computations show that three groups of inorganic ions and neutral molecules, whose structures have long been known and characterized, are aromatic due to through-space homoconjugation: (i) I(4)(2+), S(6)N(4)(2+), and S(2)I(4)(2+) dications and the (O(2))(4) cluster with pericyclic transition-state-like (PTS-like) homoaromaticity; (ii) the bishomoaromatic Te(6)(2+) and 1,5-diphosphadithiatetrazocines; and (iii) the spherically homoaromatic Te(6)(4+). The S(2)I(4)(2+) dication has an unusually high S-S bond order (approximately 2.3) and dual PTS-like aromaticity arising from two separate sets of four-center, six-electron (4c-6e) in-plane through-space conjugation. The diamagnetic (O(2))(4) structural unit recently observed in epsilon-phase oxygen solid has quadruple PTS-like aromaticity, each arising from 4c-6e in-plane through-space conjugation within an O(2)-O(2) plane. Finally, we note that the lighter S(6)(4+) and Se(6)(4+) homologues of Te(6)(4+) also are spherically homoaromatic and might be observable in complexes.

中文翻译：

主族无机分子中的同共轭/同芳香性

量子化学计算表明，三组无机离子和中性分子，其结构早已为人所知和表征，由于空间同共轭是芳香族的：（i）I（4）（2+），S（6）N（ 4)(2+) 和 S(2)I(4)(2+) dications 和 (O(2))(4) 簇具有周环过渡态样 (PTS-like) 同芳香性；(ii) 双芳香族 Te(6)(2+) 和 1,5-diphosphadithiatetrazocines；(iii) 球形同芳香族 Te(6)(4+)。S(2)I(4)(2+) dication 具有异常高的 SS 键序（约 2.3）和双 PTS 样芳香性来自两组独立的四中心六电子 (4c-6e) -平面通过空间共轭。最近在 epsilon 相氧固体中观察到的抗磁性 (O(2))(4) 结构单元具有四重 PTS 样芳香性，每个都来自 O(2)-O(2) 平面内的 4c-6e 平面内通过空间共轭。最后，我们注意到 Te(6)(4+) 的较轻的 S(6)(4+) 和 Se(6)(4+) 同系物也是球形同芳香族的，并且可能在复合物中观察到。

更新日期：2009-07-22

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