Catechol/-benzoquinone exchange at gold(iii).

Although gold(iii) chemistry has tremendously progressed in the past 2 decades, gold(iii) catecholate complexes remain extremely scarce and underdeveloped. Upon preparation and full characterization of P^C-cyclometalated gold(iii) complexes, we serendipitously uncovered an intriguing catechol exchange process at gold(iii). Electron-rich catecholates turned out to be readily displaced by electron-poor -benzoquinones. DFT calculations revealed an original path for this transformation involving two consecutive Single Electron Transfer events between the catecholate and -benzoquinone moieties while gold maintains its +III oxidation state. This catechol/-benzoquinone exchange at gold(iii) represents a new path for the exchange of X-type ligands at transition metals.