Cobalt bis(dicarbollide) ions functionalized by CMPO-like groups attached to boron by short bonds; efficient extraction agents for separation of trivalent f-block elements from highly acidic nuclear waste

Grüner, Bohumı́r; Kvı́čalová, Magdalena; Plešek, Jaromı́r; Šícha, Václav; Cı́sařová, Ivana; Lučaníková, M.; Selucký, P.

doi:10.1016/j.jorganchem.2008.11.056

Cited by 28 publications

(12 citation statements)

References 28 publications

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“…Very few reports exist on the formation of B-N bonds on cobaltabisdicarbollide [28][29][30][31][32][33][34] but no one in which the N is part of an aromatic ring. This would require overcoming an age-old challenge we had and that we have solved as described below.…”

Section: Synthesismentioning

confidence: 99%

Electron Accumulative Molecules

et al. 2018

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With the goal to produce molecules with high electron accepting capacity and low reorganization energy upon gaining one or more electrons, a synthesis procedure leading to the formation of a B-N(aromatic) bond in a cluster has been developed. The research was focused on the development of a molecular structure able to accept and release a specific number of electrons without decomposing or change in its structural arrangement. The synthetic procedure consists of a parallel decomposition reaction to generate a reactive electrophile and a synthesis reaction to generate the B-N(aromatic) bond. This procedure has paved the way to produce the metallacarboranylviologen [M(CBH)(CBH)-NCH-CHN-M'(CBH)(CBH)] (M = M' = Co, Fe and M = Co and M' = Fe) and semi(metallacarboranyl)viologen [3,3'-M(8-(NCH-CHN-1,2-CBH)(1',2'-CBH)] (M = Co, Fe) electron cumulative molecules. These molecules are able to accept up to five electrons and to donate one in single electron steps at accessible potentials and in a reversible way. By targeted synthesis and corresponding electrochemical tests each electron transfer (ET) step has been assigned to specific fragments of the molecules. The molecules have been carefully characterized, and the electronic communication between both metal centers (when this situation applies) has been definitely observed through the coplanarity of both pyridine fragments. The structural characteristics of these molecules imply a low reorganization energy that is a necessary requirement for low energy ET processes. This makes them electronically comparable to fullerenes, but on their side, they have a wide range of possible solvents. The ET from one molecule to another has been clearly demonstrated as well as their self-organizing capacity. We consider that these molecules, thanks to their easy synthesis, ET, self-organizing capacity, wide range of solubility, and easy processability, can find important application in any area where ET is paramount.

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Section: Synthesismentioning

confidence: 99%

Electron Accumulative Molecules

et al. 2018

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“…Over the past years, new type of extractants with CMPO group covalently bonded with cobalt bis(dicarbollide)(1 − ) ion have been prepared and tested in nuclear treatment [18,19]. The chlorinated cobalt bis(dicarbollide)(1 − ) with polyethylene glycol ion has been utilized for recovery 137 Cs and 90 Sr from acidic HLLW by process, originally developed in Czech Republic and leading to industrial utilization in Russia already in 1985 (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…The single charged cobalt bis(dicarbollide)(1 − ) ion [(1,2-C 2 B 9 H 10 )(1 ,2 -C 2 B 9 H 11 )-3,3 -Co(III)] (COSAN) belongs to the class of electron deficient 26-electron 12-vertex icosahedral closo borane cluster ions of extraordinary high chemical and thermal stability, hydrophobicity and inorganic super acid behaviour [21,22]. It was found that covalent bonding of COSANs ion with metal chelating group of CMPO in one single molecule significantly enhanced extraction efficiency for trivalent radionuclides from acidic solutions in comparison with "classical" CMPO ligands or their synergistic mixtures with halogenated COSANs [18,19]. Similar positive effect on enhancement of extraction efficiency for An(III) and Ln(III) was observed for other extractants of cobalt bis(dicarbollide) covalently bonded with N,N-di-n-alkyl(aryl)-diglycolamide (TODGA) groups [23] or calix [4]arenes substituted with CMPO and COSAN groups [24].…”

Section: Introductionmentioning

confidence: 99%

Separation of trivalent actinides and lanthanides from simulated high-level waste using cobalt bis(dicarbollide) ion derivate substituted with diphenyl-N-tert.octyl-carbamoylmethylphosphine oxide

Selucký¹,

Lučaníková

Grüner

2011

Radiochimica Acta

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Dicarbollide / CMPO / Liquid-liquid extraction / Actinides / Lanthanides / High level liquid wasteSummary. A derivative with cobalt bis(dicarbollide)(1 − ) ion covalently bonded with diphenyl-N-tert.octyl-carbamoylmethylphosphine oxide with a formula [(8-Ph 2 P(O)-CH 2 C(O) Co] − (CMPO-COSAN) has been evaluated for actinides(III)/lanthanides(III) separation from high level liquid waste (HLLW) from PUREX reprocessing. The procedures for HLLW treatment by CMPO-COSAN dissolved in low polar mixture of hexylmethylketone and hydrogenated tetrapropylene (HMK/TPH, 1 : 1) or polar mixture of nitrobenzene/bromoform (NB/BF, 9 : 1) were proposed. The good separation of Am(III)/Ln(III) from bulk of fission products was achieved. The trivalent radionuclides were effectively stripped from the loaded organic phase by using ammonium citrate or mixture of ammonium citrate and ammonium diethylenetriamine pentaacetate (DTPA). The co-extraction of some undesirable elements as Zr, Mo, Pd was suppressed using oxalic acid and HEDTA in extraction and a scrub steps. However, co-extraction of Ag has to be solved, yet.

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“…In the past years, several new extractants based on combinations of the cobalt bis(dicarbollide) ion(1 − ), [(1,2-C 2 B 9 H 11 ) 2 -3-Co)] − (COSAN) in single molecules with different metal chelating groups (e.g. CMPO) for the partitioning of trivalent radionuclides were developed [9,10]. The COSAN is negatively charged (1 − ) strongly hydrophobic anion that belongs to the class of electron deficient 26-electron 12-vertex icosahedral closo borane cluster family, known for its extraordinary high chemical and thermal stability, hydrophobicity and inorganic super acid behavior [11,12].…”

Section: Introductionmentioning

confidence: 99%

“…The COSAN is negatively charged (1 − ) strongly hydrophobic anion that belongs to the class of electron deficient 26-electron 12-vertex icosahedral closo borane cluster family, known for its extraordinary high chemical and thermal stability, hydrophobicity and inorganic super acid behavior [11,12]. The covalent bonding of COSAN with structural analogues of CMPO chelating groups into a single molecule significantly enhances extraction efficiency for trivalent radionuclides from nuclear waste solutions in comparison with "classical" CMPO ligands or their synergetic mixtures with halogenated COSANs [9,10]. An even more drastic increase of the extraction efficiency was observed for other extractants based on the calix [4]arene bearing combination of COSAN groups and CMPO groups.…”

Section: Introductionmentioning

confidence: 99%

Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

Lučaníková

Selucký

Rais³

et al. 2011

Proceedings in Radiochemistry

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The separation of minor actinides from high-level waste (HLW) remains a difficult problem. A wide series of compounds based on two cobalt bis(dicarbollide) ions [(1,2-C2B9H10)(1′,2′-C2B9H11)-3,3′-Co(III)]− (1) covalently bonded to a diglycolyl amide platform via diethyleneglycol connectors was prepared by reaction of the diglycolic acid dichloride with various ammonium derivatives of the ion 1 with the aim to develop new class of extractants for trivalent radionuclides from acidic waste solutions. The extractants of general formulation [{(N,N-(8-CH2-CH2O)2-1,2-C2B9H10)(1′,2′-C2B9H11)-3,3′-Co)(N,N′-R)NCOCH2}2-O]Na2 differed in substitution on the amidic nitrogen (by e.g. butyl-, hexyl-, octyl-, t-octyl-, dodecyl-, benzyl-groups). Compounds were characterized by combination of 11B, 1H and 13C NMR spectroscopy, ESI-MS, HPLC, and TLC RF. The purity of all species was better than 98%. Most of the compounds proved to be very efficient extraction agents and enabled effective extraction of europium(III) and americium(III) from nitric acid solutions. The recovery of the trivalent radionuclides from the loaded organic phase was possible by using ammonium citrate or even better by using solution of ammonium citrate and ammonium DTPA (diethylenetriamine pentaacetate).

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Cobalt bis(dicarbollide) ions functionalized by CMPO-like groups attached to boron by short bonds; efficient extraction agents for separation of trivalent f-block elements from highly acidic nuclear waste

Cited by 28 publications

References 28 publications

Electron Accumulative Molecules

Electron Accumulative Molecules

Separation of trivalent actinides and lanthanides from simulated high-level waste using cobalt bis(dicarbollide) ion derivate substituted with diphenyl-N-tert.octyl-carbamoylmethylphosphine oxide

Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

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