Supramolecular Aggregation Patterns and Stereochemical Consequences of Tellurium(Lone Pair)…π(Aryl) Interactions

Abstract

While the formation of π-aryl bonds is typical for transition metals, the main-group elements display a reduced tendency to form π -aryl complexes. This being stated, it was established by the report of the so-called "Menschutkin's complexes", for example, C 6 H 6 .SbCl 3 [1], that main-group element compounds can and do form such interactions. In the case of transition-metal systems, metal···π interactions are readily rationalised in terms of electron donation from the electron-rich aryl system to the electropositive metal centre. By contrast, allied interactions with main-group elements, often having a lone pair of electrons, seems counterintuitive. However, as indicated from macromolecular chemistry [2,3], heteroatom(lone pair)···π (aryl) interactions are stabilising. Theoretical studies indicate energies of stabilisation ranging from 1.5 to 5.1 kJ mol −1 [4,5]. The heteroatom(lone

CHAPTER 4. A New Non-Covalent Bonding Mode in Supramolecular Chemistry: Main Group Element Lone-Pair–π(arene) Interactions

“…14 More recently, a new search was undertaken and the stereochemical influence of the tellurium lone-pair interaction with the πsystems investigated. 15 The data mining of the CSD 13 was extended to practically all posttransition metals, 16 i.e. gallium, indium and thallium, 17 tin, 18 lead, 19 arsenic, 20 antimony and bismuth, 21 and selenium.…”

Selective recognition and reversible encapsulation of tetrameric alcohol clusters via hydrogen bonds using a perfluorinated dinuclear nickel(ii) complex

“…10–12 The reversible adsorption of aromatic guest molecules with concurrent color and shape changes of non-porous host crystals of fully fluorinated metal complexes was previously achieved, and the driving force of the guest insertion process was demonstrated to be a result of the formation of hydrophobic pockets surrounded by pentafluorophenyl groups. 13–15 In particular, it has been found that Cu 2+ complexes form several pseudo-polymorphic crystals incorporating benzene derivatives though enhanced intermolecular metal⋯π 13,16,17 and π-hole⋯π interaction. 18–20…”