Dissolution of elemental gold in organic solutions is ac ontemporary approach to lower the environmental burden associated with gold recycling.Herein, we describe fundamental studies on ah ighly efficient method for the dissolution of elemental Au that is based on DMF solutions containing pyridine-4-thiol (4-PSH) as ar eactive ligand and hydrogen peroxidea sa no xidant. Dissolution of Au proceeds through several elementary steps:i somerization of 4-PSH to pyridine-4-thione (4-PS), coordination with Au 0 ,and then oxidation of the Au 0 thione species to Au I simultaneously with oxidation of free pyridine thione to elemental sulfur and further to sulfuric acid. The final dissolution product is aA u I complex bearing two 4-PS ligands and SO 4 2À as ac ounterion. The ligand is crucial as it assists the oxidation process and stabilizes and solubilizes the formed Au cations.
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.
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 I 2 oxidizes Au 0 and forms a [Au I I 2 ] À species, which undergoes subsequent ligand-exchange reactions and forms a stable bis-ligand Au I complex. H 2 O 2 oxidizes free iodide and regenerated I 2 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.
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.
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