Improving the Global Electrophilicity Index (GEI) as a Measure of Lewis Acidity
Improving the Global Electrophilicity Index (GEI) as a Measure of Lewis Acidity
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DOI：
10.1021/acs.inorgchem.8b02517
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发表时间：
2018-12-03
影响因子：
4.6
通讯作者：
Stephan, Douglas W.
中科院分区：
文献类型：
--
作者：
Jupp, Andrew R.;Johnstone, Timothy C.;Stephan, Douglas W.
全球亲电性指数（GEI）已被进一步探讨作为一个通用的和无碱的度量刘易斯酸度。许多计算方法，包括后Hartree Fock，密度泛函理论和含时密度泛函理论，已被探索。以这种方式，我们寻求最适用于一系列具有不同结构和电子特征的不同刘易斯酸的方法，包括三卤化硼、四卤化硅、氟芳基硼烷和第15族五卤化物。发现最准确和计算效率最高的方法是在B3 LYP/def 2-TZVP理论水平上使用来自几何优化的轨道能量。此外，GEI显示作为一个有效的酸度度量，是互补的氟离子亲和力。GEI也被证明是一个更好的衡量刘易斯酸度的软基地，证实了比较的碘离子亲和力的15族五卤化物。
The global electrophilicity index (GEI) has been further explored as a general and base-free metric for Lewis acidity. A number of computational methods, including post-Hartree Fock, density functional theory, and time-dependent density functional theory, have been explored. In this fashion, we sought the method most applicable to a range of different Lewis acids with differing structural and electronic features, including boron trihalides, silicon tetrahalides, fluoroaryl boranes, and group 15 pentahalides. The most accurate and computationally efficient approach was found to use the energies of the orbitals from a geometry optimization at the B3LYP/def2-TZVP level of theory. In addition, the GEI is shown to act as an effective acidity metric that is complementary to the fluoride ion affinity. The GEI also proved to be a better gauge of Lewis acidity for softer bases, as confirmed by comparison to the iodide ion affinity of the group 15 pentahalides.