Outer‐Sphere Coordination Chemistry: Selective Extraction and Transport of the [PtCl<sub>6</sub>]<sup>2−</sup> Anion

Bell, Katherine J.; Westra, Arjan N.; Warr, Rebecca J.; Chartres, Jy D.; Ellis, Ross J.; Tong, Christine C.; Blake, Alexander J.; Tasker, Peter A.; Schröder, Martin

doi:10.1002/anie.200703272

Cited by 69 publications

(44 citation statements)

References 31 publications

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“…Outer-sphere interactions between the Ru complex anion and the protonated ligands can contribute the formation of stable Ru complex in the organic phase as in the previous study regarding Pt(IV) extractions [26]. …”

Section: Structural Study Of Ru Extracted By Ehbaamentioning

confidence: 64%

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Suzuki

Ogata

Tanaka

et al. 2018

Metals

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Abstract:The refining of platinum group metals is based mainly on solvent extraction methods, whereas Ru is selectively recovered by distillation as RuO 4 . Replacement of distillation by extraction is expected to simplify the purification process. To develop an effective extraction system for Ru, we analyzed the Ru species in HCl with ultraviolet-visible (UV-Vis) and Ru K-edge extended X-ray absorption fine structure (EXAFS) spectroscopies, and we examined the properties of Ru extracted with N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide) amine (EHBAA) and trioctylamine (TOA). EXAFS and UV-Vis spectra of Ru in HCl solutions revealed that the predominant Ru species in 0.5-10 M HCl solutions changed from [RuCl 4 (H 2 O) 2 ] − to [RuCl 6 ] 3− with the HCl concentration. The extraction percentages (E%) of Ru in the EHBAA system increased with increasing HCl concentration, reached 80% at [HCl] = 5 M, and decreased at higher HCl concentrations; the corresponding E% for TOA were low. EXAFS analysis of the extracted complex indicated that the Ru 3+ had 5 Cl − and 1 H 2 O in its inner coordination sphere. The similarity of the dependence on HCl concentrations of the E% in the EHBAA system and the distribution profile of [RuCl 5 (H 2 O)] 2− on [RuCl n (H 2 O) 6−n ] 3−n suggested that the EHBAA extracted the pentachlorido species.

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Section: Structural Study Of Ru Extracted By Ehbaamentioning

confidence: 64%

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Suzuki

Ogata

Tanaka

et al. 2018

Metals

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“…By increasing the extraction time up to 24 h, E% of Pt(IV) increases moderately because of the additional effect of a multidentate ligand of 1. The reason for the increased E% may be as follows: the native diethylamino group of 1 might interact with the Pt(IV) ions via inner-sphere substitution processes (30). Now, we focus on the structural mode of coordination with Pt ions, in order to clarify the extraction mechanism.…”

Section: Mechanism Of Pt(iv) Extractionmentioning

confidence: 99%

Synthesis and characterisation of p-diethylaminomethylthiacalix[4]arene for selective recovery of platinum from automotive catalyst residue

Yamada

Gandhi

Kondo

et al. 2014

Supramolecular Chemistry

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2014) Synthesis and characterisation of p-diethylaminomethylthiacalix[4]arene for selective recovery of platinum from automotive catalyst residue, Supramolecular Chemistry, 26:7-8, 620-630,The ability of chloroform solutions of p-diethylaminomethylthiacalix[4]arene 1 to extract platinum from HCl media was tested. As an ion-pair extractant, compound 1 had the highest platinum extraction ability among all the thiacalix[n] arene derivatives tested in this study. Compound 1 was a highly specific extractant for Pt(IV) ions from single-metal solutions and platinum-group metal solutions from automotive catalyst residue. Various conditions such as contact time, pH, concentration of 1, effect of chloride ions, effect of acidity and Pt(IV) concentration were studied. The distribution ratio of platinum ions (D) was calculated. The platinum complex stoichiometry ratio was obtained using slope analysis. The 1 -Pt(IV) complex was characterised using X-ray photoelectron spectroscopy, FT-IR and 1 H NMR. Finally, the Pt (IV) extraction percentage of compound 1 was compared with that of previously reported thiacalix[n]arene-based extractants.

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“…For example, organic-inorganic layered perovskites that exhibit interesting electrical (semiconducting) [11] and optical [12] properties have been synthesized [13]. Magnetic [14] and nonlinear optical [15] hybrid materials have also been designed exploiting the nucleophilic character of perhalometallates, and the judicious design of a multiple hydrogen-bond donor ligand which can encapsulate perhalometallates has been employed for the recovery of metal salts [16]. Recently, some studies on hydrogen bonded salts have demonstrated that N-H···X-M hydrogen bonds permit the formation of N-M bonds in the solid state by the elimination of gaseous HX, which will be discussed in detail in Section 5.4.5 [17,18].…”

Section: Halogens As Nucleophilesmentioning

confidence: 99%

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

Espallargas

2010

Ideas in Chemistry and Molecular Sciences

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The ultimate goal of a solid-state chemist is the rational design and synthesis of crystalline materials with the presence of specific and tunable chemical or physical properties, the so-called ''smart materials.'' Porosity, magnetism, chirality, conductivity, superconductivity, spin-transition, optical, and photophysical properties can be exploited for a wide variety of applications including gas storage, separations, electronic, catalysis, nonlinear optics, or drug delivery, and are therefore the objectives of intense research activity. The occurrence of these properties in crystalline materials 1) results from the combination of two aspects: (i) the molecular units (building blocks) that compose the crystal and (ii) the arrangement of these building blocks in the crystal. Controlling the former is relatively simple, and essentially it is only limited to the imagination and creativity of the researcher, since molecular chemistry has, over about two centuries, developed a wide range of very powerful procedures for creating even more sophisticated molecules from atoms linked by covalent bonds. On the contrary, organizing the molecules, or building blocks, in a predetermined manner is difficult to accomplish given that the structure of crystalline solids results from a delicate balance between all the intermolecular interactions present in the crystal, maximizing the attractive ones and minimizing the repulsive ones while, although not always, adopting the densest packing [1]. When a single strong interaction dominates in the system other weak intermolecular interactions normally play a secondary role in the crystal packing, providing support to the stronger interactions. In this situation, control over the molecular packing can successfully be achieved [2], although the presence of numerous weak interactions can in some cases overwhelm much stronger interactions as a result of their abundance [3]. Further difficulties can be encountered if the building blocks are 1) It should of course be acknowledged that crystalline products might not always represent the most desirable form of a material with respect to a given application.

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Outer‐Sphere Coordination Chemistry: Selective Extraction and Transport of the [PtCl₆]²⁻ Anion

Cited by 69 publications

References 31 publications

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Synthesis and characterisation of p-diethylaminomethylthiacalix[4]arene for selective recovery of platinum from automotive catalyst residue

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

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Outer‐Sphere Coordination Chemistry: Selective Extraction and Transport of the [PtCl6]2− Anion

Cited by 69 publications

References 31 publications

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Speciation of Ruthenium(III) Chloro Complexes in Hydrochloric Acid Solutions and Their Extraction Characteristics with an Amide-Containing Amine Compound

Synthesis and characterisation of p-diethylaminomethylthiacalix[4]arene for selective recovery of platinum from automotive catalyst residue

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

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Product

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Outer‐Sphere Coordination Chemistry: Selective Extraction and Transport of the [PtCl₆]²⁻ Anion