Stabilisation of Bromenium Ions in Macrocyclic Halogen Bond Complexes

Abstract

Abstract Halenium ions (X + ) are highly reactive electron deficient species that are prevalent transient intermediates in halogenation reactions. The stabilisation of these species is especially challenging, with the most common approach to sequester reactivity through the formation of bis‐pyridine (Py) complexes; [(Py) 2 X] + . Herein, we present the first example of a macrocyclic stabilisation effect for halenium species. Exploiting a series of bis‐pyridine macrocycles, we demonstrate that preorganised macrocyclic ligands stabilise bromenium cations via endotopic complexation, impressively facilitating the isolation of a bench stable ‘Br + NO 3 − ’ species. Solid state X‐ray crystallographic structural comparison of macrocyclic Br(I) complexes with Ag(I) and Au(I) analogues provides insightful information concerning similarities and stark contrasts in halenium/metal cation coordination behaviors. Furthermore, the first chemical ligand exchange reactions of Br(I) complexes are reported between acyclic [(Py) 2 Br] + species and a bis‐pyridine macrocyclic donor ligand which importantly highlights a macrocycle effect for halenium cation stabilisation in the solution phase.