Understanding the Surprising Oxidation Chemistry of Au−OH Complexes

Abstract

Au is known to be fairly redox inactive (in catalysis) and bind oxygen adducts only quite weakly. It is thus rather surprising that stable AuÀ OH complexes can be synthesized and used as oxidants for both one-and two-electron oxidations. A charged Au III À OH complex has been shown to cleave CÀ H and OÀ H bonds homolytically, resulting in a one-electron reduction of the metal center. Contrasting this, a neutral Au III À OH complex performs oxygen atom transfer to phosphines, resulting in a two-electron reduction of the hydroxide proton to form a Au III À 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 À OH. Although the current scope of known AuÀ 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.

Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d10Configurations in Formal Gold(III) Complexes

“…While the generalization that gold(I) and gold(III) may be used interchangeably as catalysts broadly holds, we do note that in certain cases divergence in the chemical behavior can be observed e.g., the oxidation chemistry of gold hydroxide complexes. [35] Angewandte Chemie…”

Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d10Configurations in Formal Gold(III) Complexes

“…While the generalization that gold(I) and gold(III) may be used interchangeably as catalysts broadly holds, we do note that in certain cases divergence in the chemical behavior can be observed e.g., the oxidation chemistry of gold hydroxide complexes. [35]…”

Influence of Different Carrier Gases, Temperature, and Partial Pressure on Growth Dynamics of Ge and Si Nanowires

“…The catalyst droplet can be obtained either as the result of dewetting a thin film [67,68], as a lithographically fabricated nanoparticle array [69,70], or by depositing a colloidal solution on the substrate [54,71,72]. Gold has proven to be an ideal catalyst for hydride precursors; it is redox-inactive [73], exhibits a relatively low eutectic temperature, and has many key semiconducting materials, including silicon and germanium. For Si and Ge in combination with Au, the eutectic temperature is around 360 • C [74][75][76][77][78][79].…”