Hayashi Satoko, Nishide Taro, Nakanishi Waro, Sancineto Luca, Santi Claudio
Faculty of Systems Engineering, Wakayama University 930 Sakaedani Wakayama 640-8510 Japan
Organic Chemistry Section, Center of Molecular and Macromolecular Studies, Polish Academy of Sciences Sienkiewicza 112 90-363 Lódz Poland.
RSC Adv. 2019 Nov 29;9(67):39435-39446. doi: 10.1039/c9ra09022c. eCollection 2019 Nov 27.
The intrinsic dynamic and static nature of G--E--Y σ(3c-4e) interactions was elucidated with the quantum theory of atoms in molecules dual functional analysis (QTAIM-DFA), employing -Me GCHCHEY (Me G = MeN and MeE; E = O, S, Se and Te; Y = F, Cl, Br, I, EMe and Me). Asterisks () are employed to emphasize the existence of bond critical points (BCPs) on the bond paths (BPs), corresponding to the interactions in question. Data from the fully optimized structure correspond to the static nature of interactions. The dynamic nature is called the intrinsic dynamic nature if the perturbed structures are generated using the coordinates derived from the compliance constants. Basis sets of the Sapporo-TZP type with diffusion functions are employed for the heteroatoms at the MP2 level. The noncovalent G--E interactions in GEY σ(3c-4e) are predicted to demonstrate van der Waals bonding to CT-TBP (trigonal bipyramidal adduct formation through charge transfer) nature, while the E--Y bonds have the covalent nature. Some E-F bonds show strong ionic character when G--E is predicted to be stronger than E--Y. The contributions of the CT terms to the G--E interactions, evaluated with NBO, are discussed in relation to the predicted nature. The (2) values based on NBO are strongly correlated to the compliance constants for the G-*-E interactions if suitably treated separately.
利用分子中原子的量子理论双功能分析（QTAIM-DFA），对G--E--Y σ(3c - 4e)相互作用的内在动态和静态性质进行了阐明，其中使用了 -Me GCHCHEY（Me G = MeN和MeE；E = O、S、Se和Te；Y = F、Cl、Br、I、EMe和Me）。星号（）用于强调键路径（BP）上键临界点（BCP）的存在，这对应于所讨论的相互作用。来自完全优化结构的数据对应于相互作用的静态性质。如果使用从柔顺常数导出的坐标生成微扰结构，那么动态性质就被称为内在动态性质。在MP2水平上，为杂原子采用带有弥散函数的札幌-TZP型基组。预测GEY σ(3c - 4e)中的非共价G--E相互作用表现出范德华键合到CT-TBP（通过电荷转移形成三角双锥加合物）的性质，而E--Y键具有共价性质。当预测G--E比E--Y更强时，一些E-F键表现出很强的离子特性。用NBO评估的CT项对G--E相互作用的贡献，结合预测的性质进行了讨论。如果分别进行适当处理，基于NBO的(2)值与G-*-E相互作用的柔顺常数高度相关。
