Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
Department of Chemistry, University of Texas at El Paso, El Paso, Texas, 79968, USA.
Angew Chem Int Ed Engl. 2016 Feb 12;55(7):2374-7. doi: 10.1002/anie.201509057. Epub 2016 Jan 14.
In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h -C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h -C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes.
在这项工作中，使用密度泛函理论计算研究了二溴代丙二酸二乙酯与 Sc3N@D3h -C78 所有非等效键的 Bingel-Hirsch 加成反应。计算中观察到的区域选择性允许提出一组规则，即预测芳香性标准 (PAC)，以便根据笼状结构的简单评估来识别给定的内嵌金属富勒烯中最具反应性的键。基于 PAC 的预测完全得到了 Sc3N@D5h -C80 的 Bingel-Hirsch 反应的计算和实验探索的证实，这表明这些规则相当通用，适用于其他孤立的五元环规则内嵌金属富勒烯。
Zotero 插件