重新审视 Paddlanes:哪些是最小的?

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Gary W. Breton
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引用次数: 0

摘要

桥链是具有四个桥链的三环分子,这些桥链共享相同的两个桥头碳原子。已知的主框架中仅含有碳原子的最小的 Paddlane 共有 18 个原子。我们利用计算化学(MP2/cc-pVTZ)找到了符合霍夫曼、施莱尔和谢弗提出的 "稍纵即逝 "标准的最小全碳 paddlanes,这意味着频率计算表明这些结构是各自势能面(PES)上的能量最小值。我们的研究结果表明,原子总数为 10 个或更少的划线化合物可以被认为是不可行的,这要么是因为它们不是势能面上的能量最小值,要么是因为系统中的应变表现为特别长的碳-碳键。一些碳原子总数为 11 个的划线被证明是能量最小值,但仍表现出比正常碳-碳键更长的碳-碳键。最后,几个碳原子总数为 12 个的配位层似乎是应变最小的,因为碳碳键的长度仍然合理。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Paddlanes revisited: Which are the smallest possible?

Paddlanes revisited: Which are the smallest possible?

Paddlanes are tricyclic molecules with four bridging chains that share the same two bridgehead carbon atoms. The smallest known paddlane containing only carbon atoms in the main framework has a total of 18 atoms. We utilized computational chemistry (MP2/cc-pVTZ) to locate the smallest possible all-carbon paddlanes that meet the criterion suggested by Hoffmann, Schleyer, and Schaefer as being “fleeting,” meaning frequency calculations suggest the structures are energy minima on their respective potential energy surfaces (PES). Our results suggest that paddlane compounds with a total of 10 or fewer atoms can be considered to be non-viable either because they are not energy minima on the PES or due to strain in the system that manifests as especially long carbon–carbon bonds. Some paddlanes with a total of 11 carbon atoms proved to be energy minima but still exhibited longer carbon–carbon bonds than normal. Finally, several paddlanes with a total of 12 carbons appear to be the least strained since carbon–carbon bond lengths remain reasonable.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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