Coordination chemistry of a para-tert-octylcalix[4]arene fitted with phosphinoyl pendant arms towards 4f-elements: Extraction, synergism, separation

Abstract

To cite this article: Maria Atanassova, Nikolay Vassilev, Emil Tashev, Victoria Lachkova & Sabi Varbanov (2015): Coordination chemistry of a para-tert-octylcalix[4] arene fitted with phosphinoyl pendant arms towards 4f-elements: extraction, synergism, separation, Separation Science and Technology, Abstract: The solvent extraction of trivalent lanthanoids (Ln 3+ ) by 5,11,17,23-tetra(para-tertoctyl)-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene (S), bearing four phosphine oxide donor groups at the lower rim as synergistic agent in combination with a 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP) in CHCl 3 from chloride medium at µ=0.1 was quantitatively described in the form of LnP 3 ·S complexes. The role of the synergistic agent on the extraction process was discussed. The values of the separation factors have been evaluated. Separation Science and TechnologyA c c e p t e d M a n u s c r i p t 2 On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid mixed complex of Eu(III) with HP and S were proposed.

Synergism as a phenomenon in solvent extraction of 4f-elements with calixarenes

“…85 A systematic attempt has been made by Atanassova and coresearchers to investigate the synergistic solvent extraction of lanthanoids with chelating molecule/calixarene combinations. [27][28][29][43][44][45][46][86][87][88] Various types of compounds, which belong to the two cyclic chemical families, Fig. 7, have been studied in order to examine the role of the chemical structure on the 4fcomplexation.…”

“…The involvement of one molecule of the phosphorus containing calix [4]arene in the synergistic species when trivalent lanthanoids are extracted with chelating extractants from 4aroyl-3-methyl-1-phenyl-pyrazol-5-one's family (HP, 43 HPMFBP and HPMMBP, 24 HPMTFBP 45 or HPPMBP 46 ) have been established independently from the number of the macrocycles, calix [4]arene, calix [6]arene and calix [8]arene, fragments on the upper 88 or lower rim. 43,44,88 The complexes with the same stoichiometry LnL 3 $S have been conrmed with combinations including HTTA and 4-tert-butylcalix [4]arene-tetraacetic acid tetraethyl ester (S8) 29 and HPBI and tert-butylcalix [4]arene tetrakis(N,N-dimethylacetamide (S7)). 87 The extraction data of La 3+ ions with HPMTFBP-S5 combination were presented in Fig.…”

Synergistic Solvent Extraction of Lanthanides(III) with Mixtures of 4-Benzoyl-3-Methyl-1-Phenyl-5-Pyrazolone and Phosphoryl-Containing Podands

“…Many studies have been carried out using phosphorus-containing calix [n] arenes as a synergistic agent at the Ln(III) extraction with various acidic chelating extractants of β-diketone type. [21][22][23][24][25][26] The introduction of P(O) functional groups in the calixarene architecture leads to a significant increase in the extraction efficiency. 26 The addition of phosphorus-containing calix [6]arene to the chelating extractant, 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone, improves the Ln(III) extraction and produces very large synergistic effects (more than five orders of magnitude).…”

Alkylation and pre-organisation of diglycolamide ligands on flexible platforms for nuclear waste treatment

“…Plutonium tracer (mainly 239 Pu) was purified from 241 Am 34 and the 233 U tracer was purified from 229 Th using standard ion-exchange methods reported before. 32 The valency of Pu was adjusted to the +4 state by using NaNO 2 and ammonium metavanadate as the holding oxidant.…”

“…On the other hand, the addition of a phosphorylcalix [4]arene increased the D values and a more hydrophobic calix [4]arene had a stronger effect. 229 In general the substituent on the benzoyl ring in pyrazolone derivatives had low influence on the extraction efficiency (only 4-trifluoromethyl had a noticeable impact on the D values, Chart 2.43). 230 This topic has also been discussed in a recent review.…”