Theoretical investigation of cheletroptic decarbonylation reactions
Theoretical investigation of cheletroptic decarbonylation reactions
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DOI：
10.1021/ct060013o
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发表时间：
2006-07-11
影响因子：
5.5
通讯作者：
Chou, Pi-Tai
中科院分区：
文献类型：
--
作者：
Lai, Chin-Hung;Li, Elise Y.;Chou, Pi-Tai
在本研究中，B3LYP用于计算双环-[2.2.1]庚-2,5-二烯-7- 1（7-降冰片二烯酮，1）及其相关的扩展融合芳香类似物2-5的脱羰反应。根据我们的结果，所有的反应都倾向于同步进行，以排出CO，形成相应的芳香烃。研究发现，反应的放热程度越高，需要克服的反应势垒就越小。此外，随着反应放热度的降低，过渡态结构离反应物更远，反应势垒增大。所得结果与哈蒙德假设和贝尔-埃文斯-波兰尼原理很好地吻合。研究预测5的活化能为27.83 kcal/mol，因此化合物5可以在400k的高温下生产并五烯。
In this study, B3LYP is used to calculate the decarbonylation reactions of the bicyclo-[2.2.1] hepta-2,5-dien-7-one (7-norbornadienone, 1) and its related extended fused aromatic analogues 2-5. On the basis of our results, all of the reactions tend to proceed synchronously to expel CO, forming the corresponding aromatic hydrocarbons. It is found that the more exothermic the reaction is, the less of a reaction barrier it needs to overcome. Moreover, upon a decrease of the reaction exothermicity, the structure of the transition state is farther away from the reactant, and the reaction barrier increases. The results agree well with the Hammond postulate as well as the Bell-Evans-Polanyi principle. Studies predict an activation energy of 27.83 kcal/mol for 5, so that the production of pentacene from compound 5 might proceed at elevated temperatures such as 400 K.