The chemistry of gold as an anion

Due to relativistic and classical shell structure effects, the 6s orbital of gold is significantly contracted and energetically stabilized. This is reflected by a strikingly high electron affinity, and a distinct tendency to adopt negatively polarized valence states. This tutorial review focuses on the chemistry of gold as an anion, displaying the integral ionic charge number of 1-. Two synthetic approaches to compounds containing monoatomic gold anions have become available: (1) reacting elemental gold with molten caesium and an oxide, e.g. Cs2O; (2) metathesis reactions involving Au- dissolved in liquid ammonia. Both procedures have proven to be rather versatile. Aurides synthesized along these routes are surveyed, in particular with respect to their structures and bonding properties.