Ligand Design for Base Metal Recovery

Tasker, Peter A.; Gasperov, Vesna

doi:10.1007/1-4020-3687-6_23

Cited by 8 publications

(5 citation statements)

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“…Calix[4]arenes, thiacalix[4]arenes and calix[4]resorcinarenes are the most widely applied scaffolds among other calix[n]arenes for embedding of different groups [ 12 , 13 , 14 , 15 ]. The stability of a cone -conformation, in turn, opens new opportunities for the preorganization of functional groups, which is of great advantage in developing of ligands and extractants [ 16 , 17 , 18 ]. The 1,3-diketone derivatives have been well-documented as both promising precursors in organic synthesis [ 19 , 20 ] and as promising compounds in drug design [ 21 , 22 ], although the greatest attention has been focused on their complex ability [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

2021

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The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure–property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging.

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Section: Introductionmentioning

confidence: 99%

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

2021

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“…This requires an extensive study of different classes of planar metal complexes to assess their electronic structure; their processability into thin films by evaporation or solution methods; their molecular packing in the solid state; the resulting intermolecular interactions, their magnetic properties, and the possibility of charge-transport properties. Phenolic oxime ligands are used extensively in extractive hydrometallurgy, − but the cooperative electronic properties in materials formed by transition metal complexes of these ligands has to date been overlooked. We have prepared homoleptic nickel(II) and copper(II) complexes using two structurally related phenolic oxime ligands, 2-hydroxy-5 -t- octylacetophenone oxime (L 1 H) and 2-hydroxy-5- n -propylacetophenone oxime (L 2 H).…”

Section: Introductionmentioning

confidence: 99%

Structural, Magnetic, and Electronic Properties of Phenolic Oxime Complexes of Cu and Ni

et al. 2011

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Square planar complexes of the type Ni(L(1))(2), Ni(L(2))(2), Cu(L(1))(2), and Cu(L(2))(2), where L(1)H = 2-hydroxy-5-t-octylacetophenone oxime and L(2)H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterized by single-crystal X-ray diffraction, cyclic voltammetry, UV/vis spectroscopy, field-effect-transistor measurements, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, and, in the case of the paramagnetic species, electron paramagnetic resonance (EPR) and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L(1))(2) contrasting with π-stacking interactions for M(L(2))(2) (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L(2))(2) but ideal paramagnetic behavior for Cu(L(1))(2) down to 1.8 K. Despite isostructural single crystal structures for M(L(2))(2), thin-film X-ray diffraction and scanning electron microscopy (SEM) revealed different morphologies depending on the metal and the deposition method (vapor or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalized ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/vis spectroscopy. The complexes M(L(2))(2) showed poor charge transport in a field-effect transistor (FET) device despite the ability to form π-stacking structures, and this provides design insights for metal complexes to be used in conductive thin-film devices.

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“…These liquid–liquid extraction systems take advantage of the relative ability of solutes to distribute between immiscible aqueous and organic phases in equilibrium. The aqueous solvent promotes dissociation of ionic species, while the organic phase contains a complex-forming extractant that combines with the target ionic species to form organo-metal complexes, with high solubility in the organic phaseand, conversely, negligible solubility in the aqueous phase. , Depending on the type of extractant, this complex formation may involve solvation, anion exchange, or cation exchange. In solvation, the extractant displaces water molecules from the coordination sphere of a metal complex; in anion exchange, an anionic metal complex from the aqueous phase displaces an anion from the organic extractant; in cation exchange, the metal cation displaces a proton from the organic extractant .…”

Section: Introductionmentioning

confidence: 99%

“…The aqueous solvent promotes dissociation of ionic species, while the organic phase contains a complex-forming extractant that combines with the target ionic species to form organo-metal complexes, with high solubility in the organic phaseand, conversely, negligible solubility in the aqueous phase. , Depending on the type of extractant, this complex formation may involve solvation, anion exchange, or cation exchange. In solvation, the extractant displaces water molecules from the coordination sphere of a metal complex; in anion exchange, an anionic metal complex from the aqueous phase displaces an anion from the organic extractant; in cation exchange, the metal cation displaces a proton from the organic extractant . The 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (HEH-EHP, commonly known as PC88A) extractant considered in this study belongs to the cationic group and is considered effective for REE recovery …”

Section: Introductionmentioning

confidence: 99%

“…In solvation, the extractant displaces water molecules from the coordination sphere of a metal complex; in anion exchange, an anionic metal complex from the aqueous phase displaces an anion from the organic extractant; in cation exchange, the metal cation displaces a proton from the organic extractant. 16 The 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (HEH-EHP, commonly known as PC88A) extractant considered in this study belongs to the cationic group and is considered effective for REE recovery. 15 Eq 1 illustrates the overall cationic exchange reaction for hydrometallurgical extraction, where M n+ represents the cation, (HA) 2 indicates the PC88A extractant, and M(HA 2 ) n represents the organometal complex.…”

Section: Introductionmentioning

confidence: 99%

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Gibbs Energy Minimization Model for Solvent Extraction with Application to Rare-Earths Recovery

Iloeje

Colón

Cresko

et al. 2019

Environ. Sci. Technol.

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The emergence of technologies in which rare-earth elements provide critical functionality has increased the demand for these materials, with important implications for supply security. Recycling provides an option for mitigating supply risk and for creating economic value from the resale of recovered materials. While solvent extraction is a proven technology for rare-earth recovery and separation, its application often requires extensive trial-and-error experimentation to estimate parameter values and determine experimental design configurations. We describe a modeling strategy based on Gibbs energy minimization that incorporates parameter estimation for required thermodynamic properties as well as process design for solvent extraction and illustrate its applicability to rare earths separation. Visualization analysis during parameter estimation revealed a linear relationship between the standard enthalpies of the extractant and respective organo-metal complexes, analogous to the additivity principle for predicting molar volumes of organic compounds. Establishing this relationship reduced the size of the parameter estimation problem and yielded good agreement between model predictions and reported equilibrium extraction data, validating the property estimates for the organic phase species. Design exploration and optimization results map the space of feasible solvent extraction column configurations and identify the set of optimal design parameter values that meet recovery and purity targets.

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Ligand Design for Base Metal Recovery

Cited by 8 publications

References 50 publications

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

Structural, Magnetic, and Electronic Properties of Phenolic Oxime Complexes of Cu and Ni

Gibbs Energy Minimization Model for Solvent Extraction with Application to Rare-Earths Recovery

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