Stereo- and Regioselectivity of Hydrogenation of a Recently Synthesized Carboncone and Its Predictive Models,The Journal of Organic Chemistry

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Stereo- and Regioselectivity of Hydrogenation of a Recently Synthesized Carboncone and Its Predictive Models
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-08-05 , DOI: 10.1021/acs.joc.2c00970
Xuyang Chen ₁ , Yuanyuan Sun ₁ , Yang Wang ₁

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Since its atomically precise synthesis in recent experiments, the carboncone molecule presents a novel example of discrete nanocarbons with promising applications, but little is known yet about its chemical properties. In this work, we present a comprehensive computational study on the hydrogenation of carboncone with a varying number of added H atoms (from 1 to 12). Unlike planar benzenoid hydrocarbons, carboncone prefers that all H atoms be added to its external, convex surface. The previous topology-based model for hydrogenated fullerenes and benzenoid hydrocarbons is shown to be no longer valid for carboncone. We here propose an extended model capable of predicting the hydrogenation regioselectivity for carboncone, which is largely governed by π delocalization. Yet the H···H repulsion at rim sites also plays an important role in adduct stability. Interestingly, some preferred addition patterns can be understood by counting the size of intact π rings upon H addition. These findings may provide insightful guidance to the functionalization of carboncones and related nanocarbons.

中文翻译：

最近合成的碳锥加氢的立体选择性和区域选择性及其预测模型

由于在最近的实验中它的原子精确合成，碳锥分子呈现了离散纳米碳的一个新例子，具有广阔的应用前景，但对其化学性质知之甚少。在这项工作中，我们对添加不同数量的 H 原子（从 1 到 12）的碳锥加氢进行了全面的计算研究。与平面苯型烃不同，carboncone 更喜欢将所有 H 原子添加到其外部凸面。先前基于拓扑的氢化富勒烯和苯烃模型被证明不再适用于碳锥。我们在这里提出了一个扩展模型，该模型能够预测碳锥的氢化区域选择性，该模型主要受 π 离域控制。然而，边缘位置的H···H排斥在加合物稳定性中也起着重要作用。有趣的是，一些优选的添加模式可以通过计算 H 添加时完整 π 环的大小来理解。这些发现可能为碳锥和相关纳米碳的功能化提供有见地的指导。

更新日期：2022-08-05

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