Why Do Cycloaddition Reactions Involving C60 Prefer [6,6] over [5,6] Bonds?
Why Do Cycloaddition Reactions Involving C60 Prefer [6,6] over [5,6] Bonds?
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DOI：
10.1002/chem.201300648
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发表时间：
2013-06-01
影响因子：
4.3
通讯作者：
Bickelhaupt, F. Matthias
中科院分区：
文献类型：
--
作者：
Fernandez, Israel;Sola, Miquel;Bickelhaupt, F. Matthias
对C60环加成反应中已知的[6，6]键优先于[5，6]键的原因进行了计算探讨。为此，本文采用新近提出的反应活化应变模型，结合能量分解分析方法，对环戊二烯与C60的DielsAlder反应进行了分析。还考虑了其他问题，如相应过渡态的芳香性。这些结果表明，控制观察到的区域选择性的主要因素是[6，6]反应路径中变形的反应物之间沿整个反应坐标的更稳定的相互作用。
The origin of the experimentally known preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 has been computationally explored. To this end, the DielsAlder reaction between cyclopentadiene and C60 has been analysed by means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method. Other issues, such as the aromaticity of the corresponding transition states, have also been considered. These results indicate that the major factor controlling the observed regioselectivity is the more stabilising interaction between the deformed reactants in the [6,6] reaction pathway along the entire reaction coordinate.