Amalgamating at the molecular level. A study of the strong closed-shell Au(i)⋯Hg(ii) interaction

Abstract

Complex {[Hg(C₆F₅)₂][Au(C₆F₅)(PMe₃)]₂}_n2 displays unsupported Au(I)⋯Hg(II) and Au(I)⋯Au(I) interactions. Its crystal structure displays a polymeric –(Au–Hg–Au–Au–Hg–Au)_n– disposition. Ab initio calculations show very strong Au(I)⋯Hg(II) and Au(I)⋯Au(I) closed-shell interactions of −73.3 kJ mol⁻¹ and −57.0 kJ mol⁻¹, respectively, which have a dispersive (van der Waals) nature and are strengthened by large relativistic effects (>20%).