The efficient separation of metals from ores and secondary sources such as electronic waste is necessary to realising circularity in metal supply. Precipitation processes are increasingly popular and are reliant on designing and understanding chemical recognition to achieve selectivity. Here we show that a simple tertiary diamide precipitates gold selectively from aqueous acidic solutions, including from aqua regia solutions of electronic waste. The X-ray crystal structure of the precipitate displays an infinite chain of diamide cations interleaved with tetrachloridoaurate. Gold is released from the precipitate on contact with water, enabling ligand recycling. The diamide is highly selective, with its addition to 29 metals in 2 M HCl resulting in 70% gold uptake and minimal removal of other metals. At 6 M HCl, complete collection of gold, iron, tin, and platinum occurs, demonstrating that adaptable selective metal precipitation is controlled by just one variable. This discovery could be exploited in metal refining and recycling processes due to its tuneable selectivity under different leaching conditions, the avoidance of organic solvents inherent to biphasic extraction, and the straightforward recycling of the precipitant.

The recycling of metals from end-of-life secondary sources such as electronic waste remains a significant environmental and technological challenge currently detrimental to the development of circular economies. The complex nature of electronic waste, containing a myriad of different elemental metals, means that sophisticated yet simple separation methods need to be developed in order to recycle these valuable and often critical metal resources. In this work simple 2 primary, secondary, and tertiary amides are appraised as reagents that selectively transport gold from aqueous to organic phases in a solvent extraction experiment. While the strength of extraction of gold from single metal solutions is ordered 3 o >2 o >1 o , the 3 o and 2 o amides are ineffective at gold transport from mixed-metal solutions of concentrations representative of smartphones due to the formation of a third, dense phase. Increasing the polarity of the organic phase can negate third phase formation but at the expense of selectivity. The identities of the species that reside in the organic and third phases have been studied by a combination of slope analysis, mass spectrometry, NMR spectroscopy, and computational methods. These techniques show that protonation of the amide L occurs at the oxygen atom, resulting in the protonated dimer HL2 + which acts as a receptor for AuCl4 − to form dynamic supramolecular aggregates in the organic phase. The characterization of a tin complex in the third phase by X-ray crystallography supports these conclusions and furthermore, suggests the preference for the chelation of the proton by two amide molecules instead of the transport of hydronium into the organic phase and its subsequent use as structural template.

Hydroarylation of enantioenriched 1,3-disubstituted allenes has the potential to proceed with axial-to-point chirality transfer to yield enantioenriched allylated (hetero)aryl compounds. However, the gold-catalysed intermolecular reaction was previously reported to occur with no chirality transfer owing to competing allene racemisation. Herein, we describe the development of the first intermolecular hydroarylations of allenes to proceed with efficient chirality transfer and summarise some of the key criteria for achieving high regio- and stereoselectivity.

The separation of gallium from iron by solvent extraction from chloride media is challenging because the anionic chloridometalates, FeCl4− and GaCl4−, display similar chemical properties. However, we report here that the selective separation of gallium from iron in HCl solution can be achieved using the dual-purpose ionic liquid methyltrioctylammonium iodide in a solvent extraction process. In this case, the reduction of Fe3+ to Fe2+ by the iodide counterion was found to inhibit Fe transport, facilitating quantitative Ga extraction by the ionic liquid with minimal Fe extraction from 2 M HCl.

The recycling of tantalum (Ta) is becoming increasingly important due to the criticality of its supply from a conflict mineral. It is used extensively in modern electronics, such as in capacitors, and so electronic waste is a potentially valuable secondary source of this metal. However, the recycling of Ta is difficult, not least because of the challenges of its leaching and subsequent separation from other metals. In this work, we show that Ta(V) halides, such as TaCl5 and TaF5, which can potentially be accessed from Ta metal upon acid halide leaching, can be recovered by solvent extraction using a simple primary amide reagent. The need for high halide concentrations in the aqueous phase implies the formation of the hexahalide salts [TaX6]− (X = F, Cl) and that an anion-swing mechanism operates. While extraction of the fluorides is poor (up to 45%), excellent extraction under chloride conditions is found (>99%) and presents an alternative route to Ta recycling.