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))

0163341 - UACH-T 20023013 RIV CH eng J - Journal Article
Plešek, Jaromír - Grüner, Bohumír - Císařová, I. - Báča, Jiří - Selucký, P. - Rais, J.
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)).
Journal of Organometallic Chemistry. Roč. 657, 1-2 (2002), s. 59-70. ISSN 0022-328X. E-ISSN 1872-8561
R&D Projects: GA ČR GA104/99/1096; GA ČR GA104/01/0142; GA ČR GA203/99/M037; GA MŠMT LN00A028
Institutional research plan: CEZ:AV0Z4032918
Keywords : carboranes * metallaboranes * liquid-liquid extraction
Subject RIV: CA - Inorganic Chemistry
Impact factor: 1.901, year: 2002

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.
Permanent Link: http://hdl.handle.net/11104/0060592