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-PhBSC10H6)AS–AS(C10H6BSPh-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 Hb(rc) were plotted versus Hb(rc) − Vb(rc)/2 for the interaction at the BCPs, where Vb(rc) 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.

More information

Identifiers

ORCID for Simon J. Coles: orcid.org/0000-0001-8414-9272

Catalogue record

Export record

Altmetrics