Hayashi Satoko, Nishide Taro, Nagata Kengo, Nakanishi Waro
Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama, 640-8510, Japan.
ChemistryOpen. 2021 Jul;10(7):656-665. doi: 10.1002/open.202100017. Epub 2021 May 2.
The intrinsic dynamic and static nature m center-n electron interactions of the σ-type σ(m c-n e) were elucidated for the Se-Se interactions in dicationic oligomers of Se(CH CH CH ) Se (1 (Se, Se)) [n (Se, Se): n=1-8], especially for m ≥6, where n (Se, Se: n=1-8) are abbreviated by n (n=1-8), respectively. QTAIM dual functional analysis (QTAIM-DFA) was applied to the interactions. Perturbed structures generated using coordinates derived from the compliance constants (C ) were employed for QTAIM-DFA. Each Se--Se in 1 and 2 has the nature of CT-TBP (trigonal bipyramidal adduct formation through CT) and Cov-w (weak covalent), respectively, which supply the starting points of the investigations. The asterisk emphasizes the existence of a bond critical point on the interaction. All Se--Se in 3 are classified by the regular closed shell (r-CS) interactions and characterized as CT-MC (molecular complex formation through CT), which are denoted as r-CS/CT-MC, except for the central interaction, of which nature is r-CS/CT-TBP. Most interactions in 4 -8 are r-CS/t-HB (typical-HB with covalency) but some are pure-CS/t-HB (t-HB with no covalency). The linear Se interactions in 2 -8 seem close to those without any limitations, since the nature of Se-*-Se inside and outside of (CH CH CH ) are very similar with each other. The linear Se interactions in 3 -8 are shown to be analyzed as σ(m c-n e: 6≤m ≤16), not by the accumulated σ(3c-4e).
针对硒（CH₂CH₂CH₂）₂硒（1（Se，Se））[n（Se，Se）：n = 1 - 8]的二价低聚物中的硒-硒相互作用，阐明了σ型σ（m c - n e）中心 - n电子相互作用的内在动态和静态性质，特别是对于m≥6的情况，其中n（Se，Se：n = 1 - 8）分别简记为n（n = 1 - 8）。将量子拓扑原子相互作用分子轨道双功能分析（QTAIM - DFA）应用于这些相互作用。使用从柔顺常数（C）导出的坐标生成的微扰结构用于QTAIM - DFA。1和2中的每个Se∙∙∙Se分别具有电荷转移 - 三角双锥（通过电荷转移形成三角双锥加合物）和共价 - 弱（弱共价）的性质，这为研究提供了起点。星号强调相互作用上键临界点的存在。3中的所有Se∙∙∙Se都归类为规则闭壳（r - CS）相互作用，并表征为电荷转移 - 分子复合物（通过电荷转移形成分子复合物），记为r - CS/CT - MC，但中心相互作用的性质是r - CS/CT - TBP。4 - 8中的大多数相互作用是r - CS/典型 - 氢键（具有共价性的典型氢键），但有些是纯闭壳/典型 - 氢键（没有共价性的典型氢键）。2 - 8中的线性硒相互作用似乎接近没有任何限制的情况，因为（CH₂CH₂CH₂）内部和外部的Se∙∙∙Se性质彼此非常相似。3 - 8中的线性硒相互作用表明应分析为σ（m c - n e：6≤m≤16），而不是通过累积的σ（3c - 4e）。
