Quantum chemical calculations with the AIM approach applied to the π-interactions between hydrogen chalcogenides and naphthalene. Issue 55 (20th May 2016)

• Record Type: Journal Article
• Authors: Hayashi, Satoko; Sugibayashi, Yuji; Nakanishi, Waro
• Is Part Of: RSC advances. Volume 6:Issue 55(2016)
• Page Start: 49651
• Page End: 49660
• Publication Date: 2016-05-20
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6ra04738f
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : The nature of π-interactions in (EH2 ) n –*–π(C10 H8 ) ( n = 1 and 2: E = O, S, Se and Te) is elucidated with QTAIM-DFA. They have the character of the vdW- nature of the pure -CS interactions, except for HHTe–*–π(C10 H8 ), which seems stronger than others. Abstract : The nature of the π–interactions in the 1 : 1 and 2 : 1 adducts of EH2 with the naphthalene π-system (E = O, S, Se and/or Te) is elucidated by applying QTAIM-DFA (QTAIM dual functional analysis). The H–*–π interactions are detected in EH2 –*–π(C10 H8 ) and (EH2 )2 –*–π(C10 H8 ) for E = S, Se and Te, whereas E–*–π interactions are in OH2 –*–π(C10 H8 ), (OH2 )2 –*–π(C10 H8 ) and HE–H–*–π(C10 H8 ) (denoted by HHE–*–C10 H8 ) (E = S, Se and Te). Asterisks * emphasize the existence of bond critical points (BCPs) on the interactions in question. H b ( r c ) are plotted versus H b ( r c ) − V b ( r c )/2 at the BCPs in QTAIM-DFA. Plots for the fully optimized structures are analyzed using the polar coordinate ( R, θ ) representation. Those containing the perturbed structures are by ( θ p, κ p ): θ p corresponds to the tangent line of the plot and κ p is the curvature. While ( R, θ ) describe the static nature, ( θ p, κ p ) represent the dynamic nature of interactions. The θ and θ p values are less than 90° for all interactions in question, examined in this work, except for θ p = 90.6° for HHTe–*–π(C10 H8 ). Therefore, all interactions examined are classified by the pure -CS (closed shell) interactions and predicted to have vdW-nature, except for HHTe–*–π(C10 H8 ), which should have the character of the typical HB-nature without covalency. The π–EB interaction in HHS–*–C10 H8 is predicted to have the border character between the vdW-nature and the typical HB-nature without covalency, since θ p = 89.8°. The nature of four interactions appeared between 2H in TeH2 and C10 H8 in TeH2 –*–π(C10 H8 ) is also clarified well using QTAIM-DFA.