Substituent effects in cubane and hypercubane: a DFT and QTAIM study
Substituent effects in cubane and hypercubane: a DFT and QTAIM study
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立方烷和超立方烷中的取代效应：DFT 和 QTAIM 研究
DOI：
10.1007/s00214-017-2144-5
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发表时间：
2017
影响因子：
1.7
通讯作者：
Fabio Pichierri
中科院分区：
文献类型：
--
作者：
湯本史明 ;サブリン エリーナ;清水伸隆;加藤龍一;フレッテリック ロバート;千田俊哉;Fabio Pichierri
利用分子中原子的量子理论和密度泛函理论，研究了不同的立方烷和超立方烷衍生物的电荷密度，其中标题烃的所有末端氢原子都被相同数量的取代基（F，Cl，Br，CH 3，和NO 2）取代.键、环和笼临界点的电荷密度的分析表明，这些取代基具有改变立方烷骨架的电荷密度的能力，从而增强其碳-碳键的应变。此外，作为立方烷笼的膨胀和收缩的函数的电荷密度的变化表明，过取代的衍生物对它们的碳笼的变形有不同的响应。单键核自旋-自旋耦合常数1 J（13 C13 C）与计算的键临界点电荷密度之间的线性相关性表明，利用该NMR参数研究笼状烃中取代基的影响是可能的.
Using the quantum theory of atoms in molecules in combination with density functional theory, we investigate the charge densities of different cubane and hypercubane derivatives in which all the terminal hydrogen atoms of the title hydrocarbons are replaced by an equal number of substituents (F, Cl, Br, CH3, and NO2). The analysis of the charge densities of the bond, ring, and cage critical points indicates that these substituents have the ability to alter the charge density of the cubane skeleton, thereby enhancing the strain of its carbon–carbon bonds. Also, the change in the charge density as a function of the expansion and contraction of the cubane cage indicates that the persubstituted derivatives respond differently to the deformation of their carbon cages. A linear correlation between the one-bond nuclear spin–spin coupling constant1J(13C13C) and the charge densities calculated at the bond critical points suggests the possibility of employing this NMR parameter for studying the effects of substituents in cage hydrocarbons.