A series of tripodal receptors designed to recognise the outer coordination sphere of the hexachlorometallate anion [PtCl(6)](2-), and thus show selectivity for ion-pair formation over chloride binding, has been synthesised and characterised. The tripodal ligands contain urea, amido or sulfonamido hydrogen-bond donors, which are aligned to bind to the regions of greatest electron density along the faces and edges of the octahedral anion. The ligand structure incorporates a protonatable bridgehead nitrogen centre that provides a positive charge to ensure the solubility of a neutral 2:1 [LH](+)/[PtCl(6)](2-) complex in water-immiscible solvents. The extraction of [PtCl(6)](2-) from acidic chloride solutions was evaluated by using a pH-swing mechanism to control the loading and stripping of the metallate anion. The ligands L(1)-L(3), L(5)-L(9), L(11)-L(13) and L(15) showed extremely high loading (up to 95% in some cases) and high selectivity for [PtCl(6)](2-) over chloride ions (present in a 60-fold excess) compared with trioctylamine, a model Alamine reagent, which, under identical conditions, only extracted 10% of the Pt(IV) anions. Generally, extraction was observed to be greater for urea-containing ligands than their amido analogues, and a quantitative recovery of platinum from feed solutions was achieved. The formation of neutral ([LH](+))(2)[PtCl(6)](2-) packages in organic media is supported by single-crystal X-ray structure determinations of [(L(2)H)(2)PtCl(6)] x 2 CH(3)CN, [(L(8)H)(2)PtCl(6)(MeOH)(2)], [(L(12)H)(2)PtCl(6)] x 2 CH(3)CN and [(L(14)H)(2)PtCl(6)], which confirm the presence of significant hydrogen bonding between the anion and urea or amido moieties of the protonated ligand and the anion. The structure of [(L(1)H)(H(3)O)PtCl(6)] x C(6)H(6) x CH(3)CN shows hydrogen bonding of a H(3)O(+) cation to the receptor and confirms that other stoichiometries are also possible, indicating that speciation in solution may be more complex.
What's on the outside? Selective extraction and transport of [PtCl6]2− from aqueous acidic solutions in the presence of excess chloride has been demonstrated through outer‐sphere coordination of the metalloanion by tripodal polyamide and polyurea receptors (see picture; Pt purple, N blue, O red, Cl green). Loading and stripping of the organic phase can be controlled by variation of the pH value of the aqueous solution.
Extraction and binding studies of [PtCl6](2-) are reported for 24 mono-, bi-, and tripodal extractants containing tris(2-aminoethyl)amine (TREN) or tris(3-aminopropyl)amine (TRPN) scaffolds. These reagents are designed to recognize the outer coordination sphere of [PtCl6](2-) and to show selectivity over chloride anion under acidic conditions. Extraction from 0.6 M HCl involves protonation of the N-center in tertiary amines containing one, two, or three urea, amide, or sulfonamide hydrogen-bond donors to set up the following equilibrium: 2L(org) + 2H(+) + [PtCl6](2-) ⇌ [(LH)2PtCl6](org). All reagents show higher Pt loading than trioctylamine, which was used as a positive control to represent commercial trialkylamine reagents. The loading of [PtCl6](2-) depends on the number of pendant amides in the extractant and follows the order tripodal > bipodal > monopodal, with urea-containing extractants outperforming amide and sulfonamide analogues. A different series of reagents in which one, two, or three of the alkyl groups in tris-2-ethylhexylamine are replaced by 3-N'-hexylpropanamide groups all show a comparably high affinity for [PtCl6](2-) and high selectivity over chloride anion in extractions from aqueous acidic solutions. (1)H NMR titration of three extractants [LH·Cl] with [(Oct4N)2PtCl6] in CDCl3 provides evidence for high selectivity for [PtCl6](2-) over chloride for tri- and bipodal extractants, which show higher binding constants than a monopodal analogue.
The purpose of the present study was to assess the effects of criminal malingering on the MMPI-2 Restructured Clinical (RC) scales. Sixty undergraduate students were given the MMPI-2 twice. One administration was conducted according to the MMPI-2 manual, and the other was given with a special set of malingering instructions specific to a prison setting. The two MMPI-2 profiles for each participant were scored for both the Basic and RC scales. Eight participants were eliminated from the data analysis due to validity (VRIN or TRIN) concerns. Data from the remaining 52 participants were analyzed using a 2×2 repeated measures ANOVA. Results showed that, as expected, the participants achieved higher MMPI-2 scores in the malingering condition. Also, participants achieved higher scores overall on the Basic scales and a significant interaction showed that participants achieved higher scores on the Basic Scales in the malingering condition than on the RC scales in that condition. These results supported prior research, indicating that malingerers produce elevated RC profiles. However, the present results also suggest that the Basic scales may be more effective in actually detecting malingerers, mainly due to the much lower ceiling on the RC scaled scores. Further implications of these findings for research and clinical work are also discussed.
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