Dynamic and Static Behavior of E–E' Bonds in Neutral and Charged Forms of HEE'H, MeEE'Me, and Cyclo‐1, 2‐EE'(CH2)3 (E, E' = O, S, Se, and Te) Elucidated by AIM Dual Functional Analysis. Issue 5 (24th June 2014)

• Record Type: Journal Article
• Authors: Hayashi, Satoko; Matsuiwa, Kohei; Miza, Hiroaki; Nakanishi, Waro
• Is Part Of: Heteroatom chemistry. Volume 25:Issue 5(2014:Sep.)
• Page Start: 449
• Page End: 472
• Publication Date: 2014-06-24
• Subjects: Heterocyclic chemistry -- Periodicals; 547.59
• DOI: 10.1002/hc.21194
• Languages: English
• ISSNs: 1042-7163

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>The nature of the E‐*‐E' bonds in neutral, monoanionic, monocationic, and dicationic forms of HEE'H (<bold>1</bold>), MeEE'Me (<bold>2</bold>), and cyclo‐1, 2‐EE'(CH<sub>2</sub>)<sub>3</sub> (<bold>3</bold>) (E, E' = O, S, Se, Te) is investigated by applying AIM (atoms‐in‐molecules method) dual functional analysis. H<sub>b</sub>(<bold>r</bold><sub>c</sub>) are plotted versus H<sub>b</sub>(<bold>r</bold><sub>c</sub>) – V<sub>b</sub>(<bold>r</bold><sub>c</sub>)/2 for the data of E‐*‐E' at bond critical points (BCPs) of fully optimized structures and perturbed structures around the fully optimized ones. Plots for the fully optimized structures are analyzed by the polar coordinate (<italic>R</italic>, θ) representation. The (θ<sub>p</sub>, κ<sub>p</sub>) parameters are derived from those of the perturbed structures: θ<sub>p</sub> corresponds to the tangent line of each plot, and κ<sub>p</sub> is the curvature. While (<italic>R</italic>, θ) correspond to the static nature, (θ<sub>p</sub>, κ<sub>p</sub>) represent the dynamic nature of interactions. The nature of E‐*‐E' in the neutral and charged species is classified by comparing their θ and θ<sub>p</sub> values with those of the standard interactions as a reference. Data for E‐*‐E' in the neutral forms of <bold>1</bold>–<bold>3</bold> appear in the shared‐shell (SS) region (180° < θ), except for MeS‐*‐TeMe (<bold>2c</bold>), which does in the regular closed‐shell (CS) region (90° < θ < 180°). The E–E' bonds in the monoanionic forms of <bold>1</bold>–<bold>3</bold> become much longer and weakened. Therefore, data of the monoanionic forms appear in the regular CS. On the other hand, the strengths of E‐*‐E' in the mono‐ and dicationic forms are almost equal to those in the neutral forms of <bold>1</bold>–<bold>3</bold> in the plots, irrespective of the shorter E‐*‐E' lengths in the cationic forms, relative to the neutral forms.</p> </abstract>