The planarity of heteroatom analogues of benzene: Energy component analysis and the planarization of hexasilabenzene. Issue 3 (21st December 2018)

• Record Type: Journal Article
• Authors: Nakamura, Taiji; Kudo, Takako
• Is Part Of: Journal of computational chemistry. Volume 40:Issue 3(2019)
• Page Start: 581
• Page End: 590
• Publication Date: 2018-12-21
• Subjects: ab initio calculations -- hexasilabenzene -- planarity -- energy components -- repulsion; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.25743
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : There are various nonplanar heteroatom analogues of benzene—cyclic 6π electron systems—and among them, hexasilabenzene (Si6 H6 ) is well known as a typical example. To determine the factors that control their planarity, quantum chemical calculations and an energy component analysis were performed. The results show that the energy components mainly controlling the planarity of benzene and hexasilabenzene are different. For hexasilabenzene, electron repulsion energy was found to be significantly important for the planarity. The application of the pseudo Jahn–Teller effect and the Carter–Goddard–Malrieu–Trinquier model for the interpretation of the planarity of the benzene analogues was also investigated. Furthermore, based on the quantitative results, it was revealed that the planarization of hexasilabenzene is realized by introducing substituents with π‐accepting ability, such as the boryl group, that bring about a reduction of the π‐electron repulsion on the silicon skeleton. © 2018 Wiley Periodicals, Inc. Abstract : Hexasilabenzene (Si6 H6 ) is well‐known as a typical example of nonplanar heteroatom analogues of benzene. The present study shows that the energy factors mainly controlling the planarity of benzene and hexasilabenzene are different. Based on the quantitative results, some strategies to systematically control the planarity of hexasilabenzene, such as utilizing the substituent effect, are suggested.