High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC₁₀H₆)SS(C₁₀H₆SPh-8')-1' with the QTAIM approach: evidence for S₄ σ(4c-6e) at the naphthalene peri-positions.

ABSTRACT: An extended hypervalent S₄ σ(4c-6e) system was confirmed for the linear ^BS-∗-^AS-∗-^AS-∗-^BS interaction in 1-(8-Ph^BSC₁₀H₆)^AS-^AS(C₁₀H₆ ^BSPh-8')-1' (1) via high-resolution X-ray diffraction determination of electron densities. The presence of bond critical points (BCPs; ∗) on the bond paths confirms the nature and extent of this interaction. The recently developed QTAIM dual functional analysis (QTAIM-DFA) approach was also applied to elucidate the nature of the interaction. Total electron energy densities H _b( r _c) were plotted versus H _b( r _c) - V _b( r _c)/2 for the interaction at the BCPs, where V _b( r _c) represents the potential energy densities at the BCP. The results indicate that although the data for an interaction in the fully optimized structure corresponds to a static nature, the data obtained for the perturbed structures around it represent the dynamic nature of the interaction in QTAIM-DFA. The former classifies the interaction and the latter characterises it. Although ^AS-∗-^AS in 1 is classified by a shared shell interaction and exhibits weak covalent character, ^AS-∗-^BS is characterized as having typical hydrogen-bond nature with covalent properties in the region of the regular closed shell interactions. The experimental results are supported by matching theoretical calculations throughout, particularly for the extended hypervalent E₄ σ(4c-6e) (E = S) interaction.

SUBMITTER: Tsubomoto Y 

PROVIDER: S-EPMC9078645 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature