Main Avenues in Gold Coordination Chemistry

Abstract

In this contribution, we provide an overview of the main avenues that have emerged in gold coordination chemistry during the last years. The unique properties of gold have motivated research in gold chemistry, and especially regarding the properties and applications of gold compounds in catalysis, medicine, and materials chemistry. The advances in the synthesis and knowledge of gold coordination compounds have been possible with the design of novel ligands becoming relevant motifs that have allowed the preparation of elusive complexes in this area of research. Strong donor ligands with easily modulable electronic and steric properties, such as stable singlet carbenes or cyclometalated ligands, have been decisive in the stabilization of gold(0) species, gold fluoride complexes, gold hydrides, unprecedented π complexes, or cluster derivatives. These new ligands have been important not only from the fundamental structure and bonding studies but also for the synthesis of sophisticated catalysts to improve activity and selectivity of organic transformations. Moreover, they have enabled the facile oxidative addition from gold­(I) to gold­(III) and the design of a plethora of complexes with specific properties.

Recent Progress on Supramolecular Luminescent Assemblies Based on Aurophilic Interactions in Solution

“…The compounds were supported by aurophilic interactions as demonstrated by single crystal X-ray analysis (Au I •••Au I contacts between ca. 3.0 and 3.3 Å) and displayed a structured and long-lived 3 IL luminescence centered at ca. 550 nm in dichloromethane.…”

“…Emission spectra of diluted samples of the complexes in water (λ exc = 376 nm) displayed a band centered at ca. 450 nm and assigned to intra-ligand 3 [π-π*(alkynyl)] emission origin. For complexes containing the phosphane PTA, namely 58, 59 and 62 (less soluble in water and therefore aggregated at spectroscopic concentrations), an additional lower energy band centered at ca.…”

“…The complexes presented an emission band with maximum at ca. 550 nm, which was assigned to triplet metal-perturbed intraligand π-π* (C≡C) transitions or 3 MMLCT transitions, with M-M contacts corresponding to intra-and intermolecular aurophilic interactions. Upon addition of the metal cations, a progressive decrease on the absorption baseline was observed, which was indicative as of disaggregation of the Au(I) complexes.…”

“…Gold(I) complexes have attracted much attention over the past decades due to their ability to assemble through aurophilic interactions [1][2][3]. This kind of non-covalent force is present when two gold(I) ions are separated by a distance which is shorter than the sum of their van der Waals radii (ca.…”

Catalytic Gold Chemistry: From Simple Salts to Complexes for Regioselective C−H Bond Functionalization

“…[35][36][37] In particular, the structure-property-reactivity relationships of different Au(I)-and Au(III)-complexes in homogeneous catalysis have been unrav-eled in various π-systems. [38][39][40][41][42][43] The robust σ-donating and weak π-accepting properties of acetylenes render the Au-coordinated acetylenes as electrophilic species. [44][45][46][47] With an electronic configuration of [Xe]4f 14 5d 10 6 s 1 for the metallic Au 0 atom, gold catalysts mostly exist in + 1 (5d 10 ) and + 3 (5d 8 ) valent states.…”