D3h C78 (金属) 富勒烯的化学反应性:由Sc3N封装诱导的区域选择性变化
Sílvia Osuna1, Marcel Swart, Josep M Campanera
1Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain.
在富勒烯中封装一个金属化物团,显著改变了它的外体反应性. 由于反应部位发生变化,Diels-Alder对内体金属烯的反应与自由烯相比产生了不同的产物.
科学领域:
- 计算化学计算化学
- 材料科学 材料科学 材料科学
- 有机化学 有机化学
背景情况:
- 富勒烯是碳的异构体,具有独特的子结构.
- 内体金属烯 (EMF) 在烯内封装原子或.
- 外形功能化修改了富勒烯的特性,但对电磁场的反应性不太了解.
研究的目的:
- 为了比较自由烯 (D3h'-C78) 与其内金属烯衍生物 (D3h-Sc3N@C78) 的外体反应性.
- 为了研究金属化物封装对迪尔斯-阿尔德 [4+2] 循环添加反应的热力学和动力学影响.
- 分析EMF形成后的完全功能化的区域选择性变化.
主要方法:
- 在BP86/TZP//BP86/DZP层面进行密度函数理论 (DFT) 计算.
- 用1,3-丁烯进行迪尔斯-阿尔德反应的热力学和运动分析.
- 研究所有非等价债券在自由和内分体富勒烯系统.
主要成果:
- 金属化物封装极大地改变了外体反应性和区域选择性.
- 在D3h'-C78和D3h-Sc3N@C78上的Diels-Alder反应产生了不同的循环载荷导管.
- 内部的Sc3N集群降低了富勒烯的整体反应性,并将反应指向不同的键.
结论:
- 在C78中封装Sc3N显著改变了其外体反应性概况.
- 迪尔斯-阿尔德反应的区域选择性因内体金属化物存在而发生了巨大的变化.
- 电磁场提供了一条控制完全功能化的途径,并创建新的分子架构.
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