A structural, spectroscopic and DFT theoretical comparison of the cis and trans isomers of a cyclohexasilane

Ernesto Ballestero-Martínez, Gerardo Antonio Rodríguez Díaz, Roberto Andrés González León, Terrance J. Hadlington, Jürgen H. Antony, Cristopher Camacho
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Abstract

We report a synthesis of the trans and cis isomers of 1,4‐di‐tert‐butyl‐2,2,3,3,5,5,6,6‐octamethyl‐1,4‐diphenylcyclohexasilane (3), together with the solid‐state structure of cis‐3. Both isomers were characterized using multinuclear NMR and UV spectroscopies and were compared based on these data, together with DFT calculations. Remarkably, we found that both isomers of 3 showcase redshifted UV maxima when compared with other known cyclosilanes. To explain this, the theoretical calculations show that the transitions involved in the excited states of trans‐3 and cis‐3 have, in addition to the expected σ conjugation component of the Si6 ring, significant π contributions of phenyl substituents. The results presented herein show the effect of the substituent’s electronic properties regarding reactivity of intermediates, reaction yield, identity, and electronic properties of novel silicon‐containing molecules.
环己硅烷顺式和反式异构体的结构、光谱和 DFT 理论比较
我们报告了 1,4- 二叔丁基-2,2,3,3,5,5,6,6-八甲基-1,4-二苯基环己硅烷 (3) 的反式和顺式异构体的合成,以及顺式-3 的固态结构。我们使用多核核磁共振和紫外光谱对这两种异构体进行了表征,并根据这些数据和 DFT 计算对它们进行了比较。值得注意的是,我们发现与其他已知的环硅烷相比,3 的两种异构体都显示出红移紫外最大值。理论计算结果表明,反式-3 和顺式-3 激发态所涉及的跃迁,除了预期的 Si6 环的σ共轭成分外,苯基取代基的π贡献也很重要。本文介绍的结果显示了取代基的电子特性对新型含硅分子的中间体反应性、反应产率、特性和电子特性的影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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