Gold: Organometallic Chemistry

Abstract

Organogold chemistry reaches back to the beginning of the twentieth century, when Grignard compounds were first reacted with chloroauric acid. Since then, the number of organogold compounds has grown rapidly and now includes species with gold in various oxidation states (0, +1, +2, and +3) and with virtually all classes of organic substituents and ligands (alkyl, alkenyl, alkynyl, ylide, heteroaryl, ylide, carbonyl, isocyanide, carbenes, alkenes, alkynes, etc.). This development was possible owing to the discovery of many new synthetic pathways that reflect the general upsurge of organometallic chemistry in the last century and to the introduction of new physical and analytical methods as routine tools for the determination of composition and structure. Incentive and motivation for organogold research were also triggered by the emerging applications of gold and its compounds in medicine and pharmacology, as well as in many areas of modern technology, with material science and homogeneous and heterogeneous catalysis as the most prominent examples. The discovery of a novel type of bonding interactions, most common between low‐valent gold atoms with a closed‐shell electronic configuration (aurophilicity), has led to a rapid growth of the supramolecular chemistry of gold. The aggregation of mononuclear compounds to give dimers, oligomers, polymers, and clusters was found to induce novel photophysical properties (luminescence etc.), which attract widespread interest. In polynuclear compounds, aurophilic bonding is responsible for unique configurations and conformations of molecules, including clustering of gold atoms around hypercoordinate carbon atoms as one of the most curious phenomena.

Structural and Chemical Effects of the PtBu2Bridge at Unsaturated Dimolybdenum Complexes Having Hydride and Hydrocarbyl Ligands

“…A seminal example of this approach was the stabilization of a metal–metal quintuple bond between Cr atoms facilitated by the steric protection provided by bulky terphenyl ligands reported in 2005 by Power and co-workers, and all the fascinating chemistry around this type of complexes developed afterward . Among the different groups used for the incorporation of sterically demanding functionalities, P-donor ligands are particularly well suited since they are, in general, readily available and have tunable and predictable electronic and steric properties . Besides the ubiquitous tertiary phosphanes (PR 3 ), other bulky organophosphorous ligands with lower coordination numbers at the P atom, such as phosphanyls (−PR 2 ) or phosphanylidenes (−PR), have also been used for the stabilization of unusual transition metal species, especially in the case of di- or polynuclear metal complexes .…”

Tetrakis(Triphenylphosphine Oxide)Lithium Di(Iodo)Aurate(I)

“…In the course of extended studies of aurophilicity effects [8] 2 ] − and studied its crystal structure. The structure of this 1 : 1 array of complex cations and anions was of interest for two reasons: 1) The cation contains one of the smallest cations, Li + , as the coordination center of the most common tertiary phosphine oxide, Ph 3 PO.…”