Computational Probing of Schleyer's Hyperconjugative Aromaticity in a Novel Designed Anion Acceptor

IF 3.4 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Journal of Computational Chemistry Pub Date : 2025-04-02 DOI:10.1002/jcc.70084

Lawen Mohammed Rasul, Morteza Rouhani, Zohreh Mirjafary

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Abstract

Quantum chemical simulations were utilized to investigate the nature of the bonding of N³⁻, P³⁻, As³⁻, O²⁻, S²⁻, Se²⁻, F⁻, Cl⁻, and Br⁻ anions with the designed anion receptor cyclopenta-2,4-diene-1,1-diylbis(borane) abbreviated as CPDB and consecutive hyperconjugative aromaticity in its cyclopentadiene ring. Various analytical tools, including quantum theory of atoms in molecules (QTAIM), Electron Localization function (ELF), and reduced density gradient (RDG) were employed to explore the interaction between the selected anions and the CPDB structure. Moreover, the changes in the bond lengths (∆BL), harmonic oscillator model of aromaticity (HOMA), and localized orbital locator purely contributed by π-orbitals (LOL-π) analyses were performed to study the hyperconjugative aromaticity upon anion accepting. The findings indicate that the anions are connected to the CPDB structure through the electron deficiency of the B atoms and can induce the aromaticity via Schleyer's hyperconjugative aromaticity to the CPBD's ring. The nature of the interactions and hyperconjugative aromaticity effect of each anion is discussed in detail.

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利用量子化学模拟研究了 N3-、P3-、As3-、O2-、S2-、Se2-、F-、Cl- 和 Br-阴离子与设计的阴离子受体环戊二烯-2,4-二烯-1,1-二基双（硼烷）（缩写为 CPDB）及其环戊二烯环中连续超共轭芳香性的键合性质。研究采用了多种分析工具，包括分子中原子量子理论（QTAIM）、电子定位功能（ELF）和还原密度梯度（RDG），来探讨所选阴离子与 CPDB 结构之间的相互作用。此外，还通过键长变化（ΔBL）、芳香度谐振子模型（HOMA）和纯粹由 π 轨道贡献的局部轨道定位器（LOL-π）分析来研究阴离子接受后的超共轭芳香度。研究结果表明，阴离子通过 B 原子的电子缺陷与 CPDB 结构相连，并能通过 Schleyer 超共轭芳香性诱导 CPBD 环的芳香性。本文详细讨论了每种阴离子的相互作用性质和超共轭芳香效应。

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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来源期刊

Journal of Computational Chemistry 化学-化学综合

CiteScore

6.60

自引率

3.30%

发文量

247

审稿时长

1.7 months

期刊介绍： This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.