Three-dimensional electron delocalization: a theoretical study based on the pentacyclo[3.3.1.13,7.01,3.05,7]decane system

Author:

Chan Mary S.W.,Arnold Donald R.

Abstract

The concept of electron delocalization, and the possibility of aromaticity in three dimensions has been introduced, but remains relatively unexplored. This work examines the structure and energy of a series of ions generated from pentacyclo[3.3.1.13,7.01,3.05,7]decane (1). The ions considered are the dication (12+), the radical cation (1+•), the radical anion (1−•), and the dianion (12−). The dication belongs to a small group of organic compounds that shows three-dimensional electron delocalization and it has been classified as "three-dimensionally homoaromatic." The relative stability of these ions is estimated by the enthalpy change of isodesmic and disproportionation reactions using energies obtained from HF, MP2, and DFT methods. The structural changes and the reorganization of the frontier orbitals when electrons are successively added to or removed from the neutral molecule (1) are also explored. The results confirm the three-dimensional electron delocalization in 12+ and indicate that it is stable relative to a localized structure with similar features; however, it is highly unstable compared to the radical cation (1+•). The dianion (12−), on the other hand, did not show any evidence for electron delocalization and it is unstable relative to the radical anion (1−•). Keywords: three-dimensional aromaticity, electron derealization, resonance, radical cations, radical anions.

Publisher

Canadian Science Publishing

Subject

Organic Chemistry,General Chemistry,Catalysis

Cited by 10 articles. 订阅此论文施引文献 订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3