Extraction of Am(III) and lanthanides(III) with organo dithiophosphinic acids

Qichu, Xu; Wu, Jianfeng; Chang, Yu-Cheng; Zhang, Lixing; Yang, Yusheng

doi:10.1524/ract.2008.1565

Cited by 25 publications

(16 citation statements)

References 13 publications

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“…11. [97][98][99][100][101][102] The affinity of polypyridyl ligands for Ln(III) ions shows a similar pattern for ligands such as tpy, MPP, DPA,(Fig. 12(a)) qpy, and DPP (Fig.…”

Section: Complexation Of F-block Metal Ions (A) the Polypyridyl Ligandsmentioning

confidence: 99%

The pyridyl group in ligand design for selective metal ion complexation and sensing

2013

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Factors in polypyridyl ligands that control their thermodynamic metal ion selectivity in aqueous solution, and their use in selective fluorescent sensing, are examined. Preorganization of polypyridyl ligands ranging from bidentate to tetradentate by bridging benzo groups, as are present in 1,10-phenanthroline (phen) compared to 2,2'-bipyridyl (bpy), is discussed. The role of solvation is considered in relation to the relative affinity of ligands containing pyridyl groups for divalent and trivalent metal ions in aqueous solution. The effects of steric clashes between H atoms on polypyridyl ligands in decreasing complex stability are evaluated, as well as the effect of chelate ring size on metal ion selectivity. Phen ligands with other donor groups present at the 2 and 9 positions, such as alcohols, amides, carboxylates, and oximes are discussed. The design of pyridyl-based ligands for the separation of Am(III) from lanthanide(III) ions is considered, as well as ligands for the removal of metal ions such as Cu(II) or Zn(II) in neurological diseases such as Alzheimer's. The design of pyridyl-based fluorescent sensors for selective sensing of metal ions is examined in terms of the role of spin-orbit coupling constants (ζ), paramagnetism, and steric effects in the development of selective fluorescent sensors that operate via chelation enhanced fluorescence (CHEF). It is concluded that for lighter metal ions with smaller ζ values such as Zn(II) and Ca(II), and to a lesser extent Cd(II), that the CHEF effect can be achieved with pyridyl-containing fluorophores that coordinate directly to the metal ion. The way in which steric effects can be used to decrease the CHEF effect in Zn(II) relative to Cd(II) to enable selective sensing of the latter is analyzed. For heavier metal ions such as Hg(II) and Pb(II), because of their large ζ values which quench fluorescence, it is concluded that the fluorophore should be tethered to the metal-binding part of the sensor, and prevented from binding to the metal ion by steric and electronic factors. How Hg(II) can quench the CHEF effect by π-contact with fluorophores such as the anthracenyl group, which at first sight might not seem able to bond with metal ions, is examined.

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“…11. [97][98][99][100][101][102] The affinity of polypyridyl ligands for Ln(III) ions shows a similar pattern for ligands such as tpy, MPP, DPA,(Fig. 12(a)) qpy, and DPP (Fig.…”

Section: Complexation Of F-block Metal Ions (A) the Polypyridyl Ligandsmentioning

confidence: 99%

The pyridyl group in ligand design for selective metal ion complexation and sensing

2013

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“…It has been shown that dithiophosphorus ligands are exceptional for this extraction as they are classified as soft-donor species [7][8][9][10][11][12][13][14]. Furthermore, dithiophosphorus ligands can be coordinated to the main group and transition metals, in particular, with soft metal centers such as palladium(II) and copper(I) [15,16].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structural characterization of Pd(II) and Cu(I) complexes containing dithiophosphorus ligand and their catalytic activities for Heck reaction

et al. 2016

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2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson's reagent) was made to react with benzylamine to produce [(PhCH2NH)(p-C6H4OMe)PS2] -[PhCH2NH3] + in a very facile manner. From the abovementioned product, two new complexes {Pd[(PhCH2NH)(p-C6H4OMe)PS2]2} (C1) and {Cu2(PPh3)2[(PhCH2NH)(p-C6H4OMe)PS2]2} (C2) were obtained in high yields whose molecular structures were ascertained by X-ray diffraction analysis, IR and NMR spectroscopy, and elemental analysis. The catalytic properties of both complexes were evaluated in the Heck reaction. High turnover numbers (TONs) and yields were observed for palladium catalyst and It was revealed that dicopper(I) complex by a distance of 2.84 Å between metal ions, bearing triphenylphosphine and dithiophosphorus ligands, can catalyze the Heck reaction. This is the first report of Cu(I) complex as catalyst in the Heck reaction. Natural bonding orbital (NBO) analysis for C1 indicated that natural charge on Pd atom is -0.07e and Pd atom has formed four sigma bonds with S atoms. Similarly, NBO analysis revealed no significant Cu…Cu interaction in dicopper complex C2.

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“…[6][7][8][9] Of the separation strategies proposed previously, 3,10-17 liquid/liquid extraction tactics relying on dithiophosphinic acids (HS 2 PR 2 ) have emerged as a promising solution to the partitioning problem. 8,[18][19][20][21][22][23][24][25] For example, HS 2 P(o-CF 3 C 6 H 4 ) 2 gives the largest Am/Eu separation factor (SF) of any extractant reported to date (SF Am/Eu = 100 000). 19 Although many variables influence the extraction process, the large separation factors observed for HS 2 P(o-CF 3 C 6 H 4 ) 2 are thought to be a consequence of greater covalency in the Am-S 2 PR 2 interactions vs. the more ionic Eu-S 2 PR 2 interactions.…”

Section: Introductionmentioning

confidence: 99%

Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

et al. 2015

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New members of the dithiophosphinic acid family of potential actinide extractants were prepared: heterocyclic 2,2'-biphenylenedithiophosphinic acids of stoichiometry HS2P(R2C12H6) (R = H or (t)Bu). The time- and atom-efficient syntheses afforded multigram quantities of pure HS2P(R2C12H6) in reasonable yields (∼60%). These compounds differed from other diaryldithiophosphinic acid extractants in that the two aryl groups were connected to one another at the ortho positions to form a 5-membered dibenzophosphole ring. These 2,2'-biphenylenedithiophosphinic acids were readily deprotonated to form S2P(R2C12H6)(1-) anions, which were crystallized as salts with tetraphenylpnictonium cations (ZPh4(1+); Z = P or As). Coordination chemistry between [S2P((t)Bu2C12H6)](1-) and [S2P(C6H5)2](1-) with U, Np, and Pu was comparatively investigated. The results showed that dithiophosphinate complexes of U(IV) and Np(IV) were redox stable relative to those of U(III), whereas reactions involving Pu(IV) gave intractable material. For instance, reactions involving U(IV) and Np(IV) generated An[S2P((t)Bu2C12H6)]4 and An[S2P(C6H5)2]4 whereas reactions between Pu(IV) and [S2P(C6H5)2](1-) generated a mixture of products from which we postulated a transient Pu(III) species based on UV-Vis spectroscopy. However, the trivalent Pu[S2P(C6H5)2]3(NC5H5)2 compound is stable and could be isolated from reactions between [S2P(C6H5)2](1-) and the trivalent PuI3(NC5H5)4 starting material. Attempts to synthesize analogous trivalent compounds with U(III) provided the tetravalent U[S2P(C6H5)2]4 oxidation product.

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Extraction of Am(III) and lanthanides(III) with organo dithiophosphinic acids

Cited by 25 publications

References 13 publications

The pyridyl group in ligand design for selective metal ion complexation and sensing

The pyridyl group in ligand design for selective metal ion complexation and sensing

Synthesis and structural characterization of Pd(II) and Cu(I) complexes containing dithiophosphorus ligand and their catalytic activities for Heck reaction

Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

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