Transannular E路路路E鈥?Interactions in Neutral, Radical Cationic, and Dicationic Forms of cyclo-[E(CH2CH2CH2)2E鈥瞉 (E, E鈥?= S, Se, Te, and O) with Structural Feature: Dynamic and Static Behavior of E路路路E鈥

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• 作者：Satoko Hayashi ; Kohei Matsuiwa ; Nozomu Nishizawa ; Waro Nakanishi
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：December 18, 2015
• 年：2015
• 卷：80
• 期：24
• 页码：11963-11976
• 全文大小：901K
• ISSN：1520-6904

文摘

The nature of the transannular E-鈭?E鈥?interactions in neutral, radical cationic, and dicationic forms of cyclo-E(CH₂CH₂CH₂)₂E鈥?(1) (E, E鈥?= S, Se, Te, and O) (1, 1^鈥?, and 1²⁺, respectively) is elucidated by applying QTAIM dual functional analysis (QTAIM-DFA). H_b(r_c) are plotted versus H_b(r_c) 鈥?V_b(r_c)/2 for the data of E-鈭?E鈥?at BCPs in QTAIM-DFA, where 鈭?emphasizes the existence of BCP. Plots for the fully optimized structures are analyzed by the polar coordinate (R, 胃) representation. Those containing the perturbed structures are by (胃_p, 魏_p): 胃_p corresponds to the tangent line of the plot, and 魏_p is the curvature. While (R, 胃) describes the static nature, (胃_p, 魏_p) represents the dynamic nature of interactions. The nature is well-specified by (R, 胃) and (胃_p, 魏_p). E-鈭?E鈥?becomes stronger in the order of 1 < 1^鈥? < 1²⁺, except for O-鈭?O. While E-鈭?E鈥?(E, E鈥?= S, Se, and Te) in 1²⁺ are characterized as weak covalent bonds, except for S-鈭?Te (MC nature through CT) and Se-鈭?Te (TBP nature through CT), O-鈭?E鈥?seems more complex. The behavior of E-鈭?E鈥?in 1²⁺ is very close to that of cyclo-E(CH₂CH₂CH₂)E鈥?(E, E鈥?= S, Se, Te, and O), except for O-鈭?O.