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首页> 外文期刊>Chemistry: A European journal >From Eight-Membered 10π Electron Sulfur-Nitrogen Cycles to Bicycles and Cages: A Theoretical Approach
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From Eight-Membered 10π Electron Sulfur-Nitrogen Cycles to Bicycles and Cages: A Theoretical Approach

机译：从八面体10π电子硫-氮循环到自行车和笼子：一种理论方法

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摘要

A simple way of rationalizing the structures of cyclic, bicyclic, and tricyclic sulfur-nitrogen species and their congeners is presented. Starting from a planar tetrasulfur tetranitride with 12π electrons, we formally derived on paper a number of heterocyclic eight-membered 10p electron species by reacting the 3p orbitals of two opposite sulfur centers with one radical each, or by replacing these centers by other atoms with five (P) or four (Si, C) valence electrons. This led to planar aromatic 10p electron systems, nonplanar bicyclic structures with a transannular S-S bond, and tricyclic structures by bridging the planar rings with an acceptor or donor unit. The final structures depend on the number of π electrons in the bridges. Intermediate biradicals are stabilized by Jahn-Teller distortion, giving transannular S-S bonds between the NSN units. This procedure may be summarized by two rules, which provide a rationale for the structures of a large number of sulfur-nitrogen-based molecules. The long bonds between the NSN units show a p character of >95 %. The qualitative results have been compared with known molecular structures and the results of B3LYP/cc-pVTZ calculations as well as CASSCF and CASVB calculations. B3LYP/cc-pVTZ calculations have also provided the UV/Vis spectra and the NICS values of the planar 10p systems.
机译：提出了一种合理化环状，双环和三环硫氮物质及其同类物结构的简单方法。从具有12π电子的平面四氮化四硫开始，我们在纸上通过将两个相对的硫中心的3p轨道各自与一个原子团反应，或将这些中心用其他五个原子取代，从而正式衍生出许多杂环的八元10p电子物种（P）或四个（Si，C）价电子。这导致了平面芳香族10p电子系统，具有跨环S-S键的非平面双环结构以及通过将平面环与受体或供体单元桥接而形成的三环结构。最终结构取决于电桥中π电子的数量。中间双自由基通过Jahn-Teller畸变而稳定，从而在NSN单元之间形成跨环S-S键。可以通过两个规则来概括该过程，这两个规则为大量基于硫-氮的分子的结构提供了理论依据。 NSN单元之间的长键显示> 95％的p特性。将定性结果与已知的分子结构，B3LYP / cc-pVTZ计算结果以及CASSCF和CASVB计算结果进行了比较。 B3LYP / cc-pVTZ计算还提供了平面10p系统的UV / Vis光谱和NICS值。

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