Understanding the Surprising Oxidation Chemistry of Au-OH Complexes.

Au is known to be fairly redox inactive (in catalysis) and bind oxygen adducts only quite weakly. It is thus rather surprising that stable Au-OH complexes can be synthesized and used as oxidants for both one- and two-electron oxidations. A charged Au ^III -OH complex has been shown to cleave C-H and O-H bonds homolytically, resulting in a one-electron reduction of the metal center. Contrasting this, a neutral Au ^III -OH complex performs oxygen atom transfer to phosphines, resulting in a two-electron reduction of the hydroxide proton to form a Au ^III -H rather than causing a change in oxidation state of the metal. We explore the details of these two examples and draw comparisons to the more conventional reactivity exhibited by Au ^I -OH. Although the current scope of known Au-OH oxidation chemistry is still in its infancy, the current literature exemplifies the unique properties of Au chemistry and shows promise for future findings in the field.
(© 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)