Transannular E center dot center dot center dot E ' Interactions in Neutral, Radical Cationic, and Dicationic Forms of cyclo-[E(CH2CH2CH2)(2)E '] (E, E ' = S, Se, Te, and O) with Structural Feature: Dynamic and Static Behavior of E center dot center dot center dot E ' Elucidated by QTAIM Dual Functional Analysis

摘要

The nature of the transannular E-*-E' interactions in neutral, radical cationic, and dicationic forms of cyclo-E(CH2CH2CH2)(2)E' (1) (E, E' = S, Se, Te, and 0) (1, 1(center dot+), and 1(2+), respectively) is elucidated by applying QTAIM dual functional analysis (QTAIM-DFA). H-b(r(c)) are plotted versus H-b(r(c)) - V-b(r(c))/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, theta) representation. Those containing the perturbed structures are by (theta(p), kappa(p)): theta(p) corresponds to the tangent line of the plot, and kappa(p) is the curvature. While (R, theta) describes the static nature, (theta(p), kappa(p),) represents the dynamic nature of interactions. The nature is well-specified by (R, theta) and (theta(p), kappa(p))). E-*-E' becomes stronger in the order of 1 < 1(center dot+) < I2+, except for O-*-O. While E-*-E' (E, E' = S, Se, and Te) in I2+ 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 I2+ is very close to that of cyclo-E(CH2CH2CH2)E' (E, E' = S, Se, Te, and O), except for O-*-O.