The Chemistry of Gold–Metal Bonds

Abstract

This chapter summarizes the preparation, structural characterization and properties of heterometallic gold compounds built through metal–metal interactions or bonds. They are mainly synthesized following four different strategies. Two of them use the acid‐base process with gold precursors acting as acids or organoaurates acting as bases, the third one consists of the use of bidentate bridging ligands, and the fourth uses the isolobal relationship between the [(R 3 P)Au] + cations and the proton in carbonyl clusters. The structural behavior of these complexes has been studied by different methods, mainly Mössbauer spectroscopy, nuclear magnetic resonance spectroscopy, and single‐crystal X‐ray diffraction. Their structures show discrete molecules, extended linear chains or even two‐ or three‐dimensional networks. Many of these complexes display luminescence and the emissions are strongly dependent on their structures. Some theoretical calculations are able to show that the formation of metal–metal interactions or bonds, as well as the gold environments, are the main aspects that affect the energy of the emissions. Other very promising areas of research such as the potential applications in electrochemistry, in biology (antiproliferative and antitumoral activity) or as homogeneous and heterogeneous catalysts are also discussed.

Terpyridine isomerism as a tool for tuning red-to-NIR emissive properties in heteronuclear gold(i)–thallium(i) complexes

“…Among them, those observed in gold derivatives are particularly frequent in coordination and organometallic complexes, which gave rise to a definite term: aurophilicity . 1 As a result of the subsequent research on heteronuclear derivatives of gold, this term soon evolved to a more general one, metallophilicity , 2 because of the increasing number of examples of heterometallic gold-containing compounds showing gold and closed-shell heterometallic centres located at distances shorter than the sum of their van der Waals radii in the solid state. These interactions have been the object of study in several laboratories both from experimental and theoretical viewpoints for many years because, in addition to their influence on the solid-state structures, they are also associated with intriguing physical and chemical properties.…”