Interconversion of au I / II / III centres in thioether macrocyclic complexes: the synthesis, structures and redox properties of [Au([18]aneS ₆ )]PF ₆ and [Au ₂ ([15]aneS ₅ ) ₂ ][B(C ₆ F ₅ ) ₄ ] ₂

The interconversion of mononuclear AuI/II/III centres in thioether macrocyclic complexes is related to the stereochemical properties of the parent AuI species; the structure of [Au([18]aneS6)]+ shows a distorted tetrahedral [2 + 2] coordination at AuI, while the AuI complex of [15]aneS5 is binuclear with AuI ions bridging [15]aneS5 ligands in a macrobicyclic structure.