Hayashi Satoko, Matsuiwa Kohei, Nishizawa Nozomu, Nakanishi Waro
Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University , 930 Sakaedani, Wakayama 640-8510, Japan.
J Org Chem. 2015 Dec 18;80(24):11963-76. doi: 10.1021/acs.joc.5b01794. Epub 2015 Dec 4.
The nature of the transannular E-∗-E' interactions in neutral, radical cationic, and dicationic forms of cyclo-E(CH2CH2CH2)2E' (1) (E, E' = S, Se, Te, and O) (1, 1(•+), and 1(2+), respectively) is elucidated by applying QTAIM dual functional analysis (QTAIM-DFA). Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 for the data of E-∗-E' at BCPs in QTAIM-DFA, where ∗ emphasizes the existence of BCP. Plots for the fully optimized structures are analyzed by the polar coordinate (R, θ) representation. Those containing the perturbed structures are by (θp, κp): θp corresponds to the tangent line of the plot, and κp is the curvature. While (R, θ) describes the static nature, (θp, κp) represents the dynamic nature of interactions. The nature is well-specified by (R, θ) and (θp, κp). E-∗-E' becomes stronger in the order of 1 < 1(•+) < 1(2+), except for O-∗-O. While E-∗-E' (E, E' = S, Se, and Te) in 1(2+) are characterized as weak covalent bonds, except for S-∗-Te (MC nature through CT) and Se-∗-Te (TBP nature through CT), O-∗-E' seems more complex. The behavior of E-∗-E' in 1(2+) is very close to that of cyclo-E(CH2CH2CH2)E' (E, E' = S, Se, Te, and O), except for O-∗-O.
通过应用量子拓扑原子相互作用分子轨道双泛函分析（QTAIM-DFA），阐明了环-E(CH₂CH₂CH₂)₂E'（1）（E、E' = S、Se、Te和O，分别对应1、1(•+)和1(2+)）的中性、自由基阳离子和二价阳离子形式中跨环E-∗-E'相互作用的本质。在QTAIM-DFA中，针对BCPs处E-∗-E'的数据，绘制了Hb(rc)与Hb(rc) - Vb(rc)/2的关系图，其中∗强调BCP的存在。通过极坐标（R, θ）表示法分析完全优化结构的图。包含扰动结构的图则通过（θp, κp）进行分析：θp对应于图的切线，κp是曲率。虽然（R, θ）描述静态本质，但（θp, κp）代表相互作用的动态本质。这种本质通过（R, θ）和（θp, κp）得到了很好的明确。除了O-∗-O外，E-∗-E'按1 < 1(•+) < 1(2+)的顺序变强。虽然1(2+)中的E-∗-E'（E、E' = S、Se和Te）除了S-∗-Te（通过电荷转移的MC本质）和Se-∗-Te（通过电荷转移的TBP本质）外都被表征为弱共价键，但O-∗-E'似乎更为复杂。除了O-∗-O外，1(2+)中E-∗-E'的行为与环-E(CH₂CH₂CH₂)E'（E、E' = S、Se、Te和O）的行为非常接近。
