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