Synthesis of symmetric dithiophosphinic acids for “minor actinide” extraction

Klaehn, John R.; Peterman, Dean R.; Harrup, Mason K.; Tillotson, Richard D.; Luther, Thomas A.; Law, Jack D.; Daniels, Lee M.

doi:10.1016/j.ica.2008.01.007

Cited by 68 publications

(69 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The downfield member of the doublet appears to be overlapped with the doublet signal of C2. The C2 signal at 132.4 ppm is a doublet with coupling of 12.3 Hz, which is comparable with similar structures [16][17][18]. The signal at 160.0 ppm belongs to the C4 ipsocarbon and is unsplit as expected.…”

Section: X-ray Studiessupporting

confidence: 81%

Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Sağlam

Çelik

Yılmaz

et al. 2010

Transition Met Chem

View full text Add to dashboard Cite

Thionation of 3-methylbutylmagnesium bromide with Lawesson's Reagent (LR) gave 4-methoxyphenyl (3-methylbutyl)dithiophosphinic acid (DTPA), and the latter was converted to the ammonium salt (NH 4 L = Ammonium 4-methoxyphenyl (3-methylbutyl) dithiophosphinate). The complex, trans-bis[4-methoxyphenyl(3-methylbutyl) dithiophosphinato] nickel(II) [NiL 2 ], was prepared by the reaction of NH 4 L with NiCl 2 .6H 2 O in EtOH. Bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) [(CoL 2 ) 2 ] was also prepared in the same way. The structures of the complexes have been characterized by elemental analysis, FTIR, 1 H, 13 C, 31 P NMR and X-ray diffraction. The single crystal X-ray structures of [NiL 2 ] and [(CoL 2 ) 2 ] show that the nickel complex is square planar while the cobalt counterpart has tetrahedral coordination with a dimeric structure. Bond lengths, angles, torsion angles and dihedral angles are correlated to the structures and also compared with the literature data on similar compounds.

show abstract

Section: X-ray Studiessupporting

confidence: 81%

Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Sağlam

Çelik

Yılmaz

et al. 2010

Transition Met Chem

View full text Add to dashboard Cite

show abstract

“…Since the discovery of the high performance of Cyanex301 in Ln III /An III separation, numerous studies have been conducted to extend the application of this system by using similar ligands or different aqueous/solvent compositions. [12][13][14][15][16][17][18][19][20][21] Moreover, efforts with different techniques have been made by several groups to understand the chemical driving force.…”

Section: Introductionmentioning

confidence: 99%

Interactions of Bis(2,4,4‐trimethylpentyl)dithiophosphinate with Nd^III and Cm^III in a Homogeneous Medium: A Comparative Study of Thermodynamics and Coordination Modes

Rao

2014

Chemistry A European J

View full text Add to dashboard Cite

Complexation of Nd(III) and Cm(III) with purified Cyanex301 (ammonium bis(2,4,4-trimethylpentyl)dithiophosphinate, denoted as HL) was studied in 1 % v/v water/ethanol under identical conditions by spectrophotometry and microcalorimetry. For Nd(III) , three successive complexes, NdL(2+) , NdL2 (+) , and NdL3 , formed in the solution. In contrast, four complexes, CmL(2+) , CmL2 (+) , CmL3 , and CmL4 (-) formed during the titration with Cm. Fluorescence lifetime measurements provided additional insight into the complexation of Cm(III) with Cyanex301. The stepwise stability constants for the CmLj ((3-j)+) (j=1-3) complexes are about one order of magnitude higher than the corresponding NdLj ((3-j)+) complexes. The enthalpies of complexation are endothermic for both Nd(III) and Cm(III) , suggesting that the energy required for desolvation exceeds the energy gained from the cation/ligand combination. Specifically, the enthalpy of complexation for CmL(2+) is 3.5 kJ mol(-1) less endothermic than that of NdL(2+) , implying stronger covalent interaction in CmL(2+) than NdL(2+) . However, the enthalpies of complexation for CmL2 (+) and NdL2 (+) are nearly identical, and the enthalpy of complexation for CmL3 (aq) becomes more endothermic than that for NdL3 (aq). The observations suggest that, in the ethanol/water media, the overall energetics of the Cm(III) /Nd(III) complexation with Cyanex301 could depend on a number of factors, including the extent of covalency, the degree of desolvation, and the coordination modes.

show abstract

“…One of the aromatic type ditiophosphinic acids (R2PS2H: DPAH), bis(o-trifluoro methylphenyl) DPAH (Fig. 14) can selectively separate Am 3+ from Eu 3+ with separation factors of ∼ 100 000 at low pH region [115].…”

Section: Sulfur Donor Extractantsmentioning

confidence: 99%

Production and properties of transuranium elements

Nagame¹,

Hirata

2011

Radiochimica Acta

View full text Add to dashboard Cite

Actinides / Syntheses / Electronic structure / Physical and chemical properties Summary. We summarize historical perspective of the transuranium elements, neptunium (Np) through lawrencium (Lr), and recent progress on production, and nuclear and chemical properties of these elements. Exotic decay properties of heavy nuclei are also introduced. Chemical properties of transuranium elements in aqueous and solid states are summarized based on the actinide concept.

show abstract

Synthesis of symmetric dithiophosphinic acids for “minor actinide” extraction

Cited by 68 publications

References 53 publications

Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Interactions of Bis(2,4,4‐trimethylpentyl)dithiophosphinate with Nd^III and Cm^III in a Homogeneous Medium: A Comparative Study of Thermodynamics and Coordination Modes

Production and properties of transuranium elements

Contact Info

Product

Resources

About

Synthesis of symmetric dithiophosphinic acids for “minor actinide” extraction

Cited by 68 publications

References 53 publications

Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Interactions of Bis(2,4,4‐trimethylpentyl)dithiophosphinate with NdIII and CmIII in a Homogeneous Medium: A Comparative Study of Thermodynamics and Coordination Modes

Production and properties of transuranium elements

Contact Info

Product

Resources

About

Interactions of Bis(2,4,4‐trimethylpentyl)dithiophosphinate with Nd^III and Cm^III in a Homogeneous Medium: A Comparative Study of Thermodynamics and Coordination Modes