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Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions
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SYSNO ASEP 0163344 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Ostatní články Title Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions Author(s) Grüner, Bohumír (UACH-T) RID, SAI, ORCID
Plešek, Jaromír (UACH-T)
Báča, Jiří (UACH-T)
Císařová, I. (CZ)
Dozol, J. F. (FR)
Rouquette, H. (FR)
Vinas, C. (ES)
Selucký, P. (CZ)
Rais, J. (CZ)Source Title New Journal of Chemistry. - : Royal Society of Chemistry - ISSN 1144-0546
Roč. 26, č. 10 (2002), s. 1519-1527Number of pages 9 s. Language eng - English Country FR - France Keywords LIQUID-CHROMATOGRAPHIC SEPARATIONS ; BORON-CLUSTER COMPOUNDS ; CALIXARENES Subject RIV CA - Inorganic Chemistry R&D Projects GA104/99/1096 GA ČR - Czech Science Foundation (CSF) GA104/01/0142 GA ČR - Czech Science Foundation (CSF) GA203/99/M037 GA ČR - Czech Science Foundation (CSF) LN00A028 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) CEZ AV0Z4032918 - UACH-T Annotation A new series of boron substituted cobalt bis(dicarbollide) (1-) ion (1) derivatives of the general formula [(8-CMPO- (CH2-CH2O)2-1,2-C2B9H10) (1', 2'-C2B9H11)-3,3'-Co] (CMPO = Ph2P(O) - CH2C(O) NR, R = C4H9 (3b), - C12H25 (4b), - CH2-C6H5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenylphosphorylacetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of B-11 NMR, H-1 high field NMR, Mass Spectrometry with Electrospray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln(3+) complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(III) atom is bonded to three functionalised cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. Workplace Institute of Inorganic Chemistry Contact Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Year of Publishing 2003
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