Functionalized cobalt bis(dicarbollide) ions as selective extraction reagents for removal of M2+ and M3+ cations from nuclear waste, crystal and molecular structures of the [8,8 '-mu-CIP(O)(O)(2)(1,2-C2B9H10)(2)-3,3 '-Co]HN(C2H5)(3) and [8,8 '-mu-Et2NP(O)(O)(2) (1,2-C2B9H10)(2)-3,3 '-Co](HN(CH3)(3))

Plešek, Jaromír; Grüner, Bohumír; Císařová, I.; Báča, Jiří; Selucký, P.; Rais, J.

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Functionalized cobalt bis(dicarbollide) ions as selective extraction reagents for removal of M2+ and M3+ cations from nuclear waste, crystal and molecular structures of the [8,8 '-mu-CIP(O)(O)(2)(1,2-C2B9H10)(2)-3,3 '-Co]HN(C2H5)(3) and [8,8 '-mu-Et2NP(O)(O)(2) (1,2-C2B9H10)(2)-3,3 '-Co](HN(CH3)(3))

1.

SYSNO ASEP	0163341
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Ostatní články
Title	Functionalized cobalt bis(dicarbollide) ions as selective extraction reagents for removal of M2+ and M3+ cations from nuclear waste, crystal and molecular structures of the [8,8 '-mu-CIP(O)(O)(2)(1,2-C2B9H10)(2)-3,3 '-Co]HN(C2H5)(3) and [8,8 '-mu-Et2NP(O)(O)(2) (1,2-C2B9H10)(2)-3,3 '-Co](HN(CH3)(3))
Author(s)	Plešek, Jaromír (UACH-T) Grüner, Bohumír (UACH-T)_{RID, SAI, ORCID} Císařová, I. (CZ) Báča, Jiří (UACH-T) Selucký, P. (CZ) Rais, J. (CZ)
Source Title	Journal of Organometallic Chemistry. - : Elsevier - ISSN 0022-328X Roč. 657, 1-2 (2002), s. 59-70
Number of pages	12 s.
Language	eng - English
Country	CH - Switzerland
Keywords	carboranes ; metallaboranes ; liquid-liquid extraction
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	New reliable synthetic methods leading to derivatives of the closo-[(1,2-C2B9H11)(2)-3,3'-Co](-) (1) anion 1 with phosphorus containing substituents on the cage boron atoms have been successfully developed, starting from its 8-OH (2) and 8,8'-(OH)(2) (3) hydroxyderivatives. Reactions of 2 with either Cl3PO or PhCl2PO followed by hydrolysis gave 8-(HO)(2)PO-O- (4) and [(8-PhPO(OH) -O)- 1,2-C2B9H10)(1,2-C2B9H11)-3,3'-Co](-) (5) phosphorylated species, respectively. Analogous reactions Of Cl3PO with 3 provided a chlorine bearing bridged product [8,8'-mu-ClP(O)(O)(2) < (1,2-C2B9H10)(2)-3,3'-Co](-) (6) with surprisingly high hydrolytic stability. The anticipated anion [8,8'-mu-(HO)(O)-P(O)(2) < (1,2-C2B9H10)(2)-3,3'-Co](-) (7) with phosphoric acid as the bridging substituent was obtained after alkaline hydrolysis of compound 6. The related [8,8'-mu-Ph(O)P(O)(2) < (1,2-C2B9H10)(2)-3,3'-Co](-) (8) derivative was prepared by similar reaction of 3 with PhCl2PO and subsequent hydrolysis. Further developments starting from versatile precursor 6 led to synthesis of a derivative containing an asymmetric bridging diethylphosporamide moiety [8,8'-mu-(Et2N)P(O)(O)(2) < (1,2-C2B9H10)(2)-3,3'-Co](-) (9). A crystal of the compound 9 containing a pure enantiomer was selected, and its absolute configuration was determined by X-ray diffraction. Molecular structure of the compound 6 was also determined by X-ray diffraction analysis and the crystallographic results for both compounds are presented. Compounds 6 and 7 represent efficient Eu3+ extractants, enabling metal extraction even from highly acidic solutions (up to 1 M HNO3) to aromatic solvents. The novel compounds thus amalgamate in the single molecule good extraction properties of cobalta bis(dicarbollide) anion and the complexation ability of alkylphosphates.
Workplace	Institute of Inorganic Chemistry
Contact	Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931
Year of Publishing	2003

Number of the records: 1