The Lewis-acidic character and robustness of NHC-Au(I) complexes enable them to catalyze a large number of reactions, and they are enthroned as the catalysts of choice for many transformations among polyunsaturated substrates. More recently, Au(I)/Au(III) catalysis has been explored either by utilizing external oxidants or by seeking oxidative addition processes with catalysts featuring pendant coordinating groups. Herein, we describe the synthesis and characterization of N-heterocyclic carbene (NHC)-based Au(I) complexes, with and without pendant coordinating groups, and their reactivity in the presence of different oxidants. We demonstrate that when using iodosylbenzene-type oxidants, the NHC ligand undergoes oxidation to afford the corresponding NHC=O azolone products concomitantly with quantitative gold recovery in the form of Au(0) nuggets ~0.5 mm in size. The latter were characterized by SEM and EDX-SEM showing purities above 90%. This study shows that NHC-Au complexes can follow decomposition pathways under certain experimental conditions, thus challenging the believed robustness of the NHC-Au bond and providing a novel methodology to produce Au(0) nuggets.
Keywords: Au(0) nuggets; NHC-Au(I) complexes; iodosylbenzene-type oxidants; oxidized NHC=O compounds; pendant ligands.