RESUMEN

Gold is a scarce element in the Earth's crust but indispensable in modern electronic devices. New, sustainable methods of gold recycling are essential to meet the growing eco-social demand of gold. Here, we describe a simple, inexpensive, and environmentally benign dissolution of gold under mild conditions. Gold dissolves quantitatively in ethanol using 2-mercaptobenzimidazole as a ligand in the presence of a catalytic amount of iodine. Mechanistically, the dissolution of gold begins when I2 oxidizes Au0 and forms a [AuI I2 ]- species, which undergoes subsequent ligand-exchange reactions and forms a stable bis-ligand AuI complex. H2 O2 oxidizes free iodide and regenerated I2 returns back to the catalytic cycle. Addition of a reductant to the reaction mixture precipitates gold quantitatively and partially regenerates the ligand. We anticipate our work will open a new pathway to more sustainable metal recycling with the utilization of just catalytic amounts of reagents and green solvents.

RESUMEN

Invited for the cover of this issue is the group of Timo Repo at the University of Helsinki. The image depicts a ligand-exchange reaction as a battle between hummingbirds and golden birds, which represent two different thiol ligands. Read the full text of the article at 10.1002/chem.202101028.

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RESUMEN

Development of new, environmentally benign dissolution methods for metallic gold is driven by needs in the circular economy. Gold is widely used in consumer electronics, but sustainable and selective dissolution methods for Au are scarce. Herein, we describe a quantitative dissolution of gold in organic solution under mild conditions by using hydrogen peroxide as an oxidant. In the dissolution reaction, two thiol ligands, pyridine-4-thiol and 2-mercaptobenzimidazole, work in a cooperative manner. The mechanistic investigations suggest that two pyridine-4-thiol molecules form a complex with Au0 that can be oxidized, whereas the role of inexpensive 2-mercaptobenzimidazole is to stabilize the formed AuI species through a ligand exchange process. Under optimized conditions, the reaction proceeds vigorously and gold dissolves quantitatively in two hours. The demonstrated ligand-exchange mechanism with two thiols allows to drastically reduce the thiol consumption and may lead to even more effective gold dissolution methods in the future.

RESUMEN

Herein we report a unique method for preparing diaryl hydroxyl dicarboxylic acids in a diastereospecific manner. The three-component reaction occurs between amino acid, aromatic aldehyde, and primary alcohol in alkaline solutions under microwave-assisted conditions. The dicarboxylic acids are isolated as sodium salts in high yields (up to 77%) by direct precipitation from the reaction solution. The experimental results suggest that the diastereospecificity originates from a [3,3]-sigmatropic rearrangement followed by a sodium-assisted hydride transfer. As further shown, the previously unreported dicarboxylic acids are easily turned into corresponding δ-lactones.

RESUMEN

Dissolution of elemental gold in organic solutions is a contemporary approach to lower the environmental burden associated with gold recycling. Herein, we describe fundamental studies on a highly efficient method for the dissolution of elemental Au that is based on DMF solutions containing pyridine-4-thiol (4-PSH) as a reactive ligand and hydrogen peroxide as an oxidant. Dissolution of Au proceeds through several elementary steps: isomerization of 4-PSH to pyridine-4-thione (4-PS), coordination with Au0 , and then oxidation of the Au0 thione species to AuI simultaneously with oxidation of free pyridine thione to elemental sulfur and further to sulfuric acid. The final dissolution product is a AuI complex bearing two 4-PS ligands and SO4 2- as a counterion. The ligand is crucial as it assists the oxidation process and stabilizes and solubilizes the formed Au cations.