Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

Heterodinuclear uranyl/group 14 complexes of the aryl- and anthracenyl-linked Schiff-base macrocyclic ligands LMe and LA were synthesised by reaction of UO2(H2L) with M{N(SiMe3)2}2 (M = Ge, Sn, Pb). For complexes of the anthracenyl-linked ligand (LA) the group 14 metal sits out of the N4-donor plane by up to 0.7 Å resulting in relatively short M⋯OUO distances which decrease down the group; however, the solid state structures and IR spectroscopic analyses suggest little interaction occurs between the oxo and group 14 metal. In contrast, the smaller aryl-linked ligand (LMe) enforces greater interaction between the metals; only the PbII complex was cleanly accessible although this complex was relatively unstable in the presence of HN(SiMe3)2 and some organic oxidants. In this case, the equatorial coordination of pyridine-N-oxide causes a 0.08 Å elongation of the endo UO bond and a clear interaction of the uranyl ion with the Pb(II) cation in the second donor compartment

Controlled and sequential single-electron reduction of the uranyl dication

A flexible tripodal pyrrole-imine ligand (H3L) has been used to facilitate the controlled and sequential single-electron reductions of the uranyl dication from the U(vi) oxidation state to U(v) and further to U(iv), processes that are important to understanding the reduction of uranyl and its environmental remediation. The uranyl(vi) complexes UO2(HL)(sol) (sol = THF, py) were straightforwardly accessed by the transamination reaction of H3L with UO2{N(SiMe3)2}2(THF)2 and adopt ‘hangman’ structures in which one of the pyrrole-imine arms is pendant. While deprotonation of this arm by LiN(SiMe3)2 causes no change in uranyl oxidation state, single-electron reduction of uranyl(vi) to uranyl(v) occurred on addition of two equivalents of KN(SiMe3)2 to UO2(HL)(sol). The potassium cations of this new [UVO2(K2L)]2 dimer were substituted by transmetalation with the appropriate metal chloride salt, forming the new uranyl(v) tetra-heterometallic complexes, [UVO2Zn(L)(py)2]2 and [UVO2Ln(Cl)(L)(py)2]2 (Ln = Y, Sm, Dy). The dimeric uranyl(v)-yttrium complex underwent further reduction and chloride abstraction to form the tetrametallic U(iv) complex [UIVO2YIII(py)]2, so highlighting the adaptability of this ligand to stabilise a variety of different uranium oxidation states.</p

Tuneable separation of gold by selective precipitation using a simple and recyclable diamide

The separation of metals from electronic waste is an enduring technological and societal challenge, and new metal extraction, refining and recycling solutions are needed. Here the authors report a recyclable and tuneable chemical reagent that separates valuable metals such as gold by direct and selective precipitation from various acidic, mixed-metal solutions of relevance to extraction and recycling industries

Uranyl to Uranium(IV) Conversion through Manipulation of Axial and Equatorial Ligands

The controlled manipulation of the axial oxo and equatorial halide ligands in the uranyl dipyrrin complex, UO2Cl(L), allows the uranyl reduction potential to be shifted by 1.53 V into the range accessible to naturally occurring reductants that are present during uranium remediation and storage processes. Abstraction of the equatorial halide ligand to form the uranyl cation causes a 780 mV positive shift in the UV/UIV reduction potential. Borane functionalization of the axial oxo groups causes the spontaneous homolysis of the equatorial U–Cl bond and a further 750 mV shift of this potential. The combined effect of chloride loss and borane coordination to the oxo groups allows reduction of UVI to UIV by H2 or other very mild reductants such as Cp*2Fe. The reduction with H2 is accompanied by a B–C bond cleavage process in the oxo-coordinated borane

Radical Relatives: Facile Oxidation of Hetero-Diarylmethene Anions to Neutral Radicals

Furan and thiophene diarylmethenes are potential redox-active ligands for metal centers that could be exploited in the development of nontraditional, stoichiometric, and catalytic redox reactions. As such, we describe here the selective <i>meso</i>-deprotonations of dithiophene, difuran, and diimine–difuran diarylmethanes to form the π-conjugated anions, for which only the diimino–difuryl anion is truly isolable and studied by X-ray crystallography. In all cases, facile one-electron oxidation of these anions occurs, which allows the isolation of the neutral dithienyl and diimino–difuryl radicals. UV–Visible and time-dependent density functional theory studies reveal that the oxidation of the dithienyl anion to its radical is associated with an increase in the highest (singly) occupied molecular orbital–lowest unoccupied molecular orbital gap, evident through a hypsochromic shift of the main absorption band in the electronic spectrum, whereas oxidation of the diimino–difuryl anion causes only minor spectroscopic changes. Electrochemical studies support the stability of the radicals with respect to the anion, showing strongly negative oxidation potentials. The control of the redox activity of these diarylmethene carbanions through variation of the nature of the substituents, donor-atom, and the conjugated π-system and their potential as ligands for redox-inert metal centers makes them intriguing candidates as noninnocent partners for redox reactions

Optimization of process parameters for the selective leaching of copper, nickel and isolation of gold from obsolete mobile phone PCBs

The sequential separation of base and precious metals from the end-of-life mobile phone printed circuit boards (PCBs) is a significant challenge for the development of recycling process that exhibit material circularity. In this contribution, a simple, eco-friendly, and efficient leaching process is developed for the dissolution of copper and nickel from obsolete mobile phone PCBs to facilitate the isolation of a gold-rich residue. Chemical pre-treatment of downsized PCBs produced a metallic portion for which the leaching parameters for copper and nickel were optimised, including the type of leaching reagent, temperature, time, pulp density and agitation speed. It was found that quantitative dissolution of base metals occurred using 3.0 M nitric acid at 30 °C with a 50 g/L pulp density, 2 h residence time, and 500 rpm stirring speed; under these conditions, no gold was dissolved. Design of Experiment analysis using Response Surface Methodology was also undertaken to validate the process. Finally, the kinetics of the leaching process were studied and shown to conform to the chemically controlled surface reaction model, with activation energies of 39.7 and 18.4 kJ/mol for copper and nickel. Importantly, the leaching process optimised in this work avoids the need for high temperatures and reduces energy consumption and effluent generation, leading to the cleaner processing of obsolete mobile phone PCBs for the separation of gold from the dominant base metals

Challenges and opportunities in the recovery of gold from electronic waste

Rapid global technological development has led to the rising production of electronic waste that presents both challenges and opportunities in its recycling. In this review, we highlight the value of metal resources in the printed circuit boards (PCBs) commonly found in end-of-life electronics, the differences between primary (ore) mining applications and secondary (‘urban’) mining, and the variety of metallurgical separations, in particular those that have the potential to selectively and sustainably recover gold from waste PCBs