Thenoyltrifluoroacetonate lanthanide

Thenoyltrifluoroacetone(TTA), C4H3S,CO,CH2,COCF3. This is a crystalline solid, m.p. 43 °C it is, of course, a /1-diketone, and the trifluoromethyl group increases the acidity of the enol form so that extractions at low pH values are feasible. The reactivity of TTA is similar to that of acetylacetone it is generally used as a 0.1-0.5 M solution in benzene or toluene. The difference in extraction behaviour of hafnium and zirconium, and also among lanthanides and actinides, is especially noteworthy. 

A broad range of metal centers have been used for the complexation of functional ligands, including beryllium [37], zinc, transition metals such as iridium [38], and the lanthanide metals introduced by Kido [39], especially europium and terbium. Common ligands are phenanthroline (phen), bathophenanthrolin (bath), 2-phenylpyridine (ppy), acetylacetonate (acac), dibenzoylmethanate (dbm), and 11 thenoyltrifluoroacetonate (TTFA). A frequently used complex is the volatile Eu(TTFA)3(phen), 66 [40]. 

Meguro, Y., Kitatsuji, Y., and Yoshida, Z. (1997) Synergistic extraction of actinides(III) and lanthanides(III) with thenoyltrifluoroacetone and crown ethers, Recent Progress in Actinides Separation Chemistry, Proceedings of the Workshop on Actinides Solution Chemistry, WASC 94, Tokai, Japan, Sept. 1-2, 1994, 53-71. 

The luminescence property of various lanthanide (3-diketonates has been reviewed (Binne-mans, 2005). In early works, 2-naphthoyltrifluoroacetone ((3-NTA), 2-thenoyltrifluoroacetone (TTA) and pivaloyltrifluoroacetone (PTA) (scheme 2) were found to be the best ligands for... 

Since the chemistry of actinium is confined to the Ac + ion, it can readily be separated from thorium (and the lanthanides, for that matter) by processes like solvent extraction with thenoyltrifluoroacetone (TTFA) and by cation-exchange chromatography. The latter is an excellent means of purification, as the Ac + ion is much more strongly bound by the resin than its decay products. 

Similar to the Sr example, lanthanide extraction into ILs has been reported to yield different structures than when prepared with an organic solvent instead the IL. In ILs, the formation of anionic Nd(tta)4 or Eu(tta)4 (Htta = 2-thenoyltrifluoroacetone) complexes with no water coordinated to the metal center is preferred. In nonpolar organic solvents, hydrated, neutral complexes, M(tta)3(H20)M (n = 2 or 3) form [162],... 

Figure 2.21 Structure of the lanthanide complexes [L (tta)3L2] (a) and [L (bta)3L2] (b). Ln represents a trivalent lanthanide ion, tta is 2-thenoyltrifluoroacetonate, bta is benzoyltrifluoroacetonate, and L is a Schiff base...

The mass spectra of the lanthanide complexes of thenoyltrifluoroacetone, [R(CF3C0CHC0C4H3S)3], have been obtained for samarium, europium, gadolinium, and terbium (Das and Livingstone, 1975). The spectra are similar and fluorine migration to the metal ion with concomitant loss of CF2 occurs. The species RFJ was observed for samarium, gadolinium, and terbium and RF was observed for the easily reduced ions samarium and europium. No oxidation of terbium to terbium(IV) occurred. A mechanism for the fragmentation has been presented. 

Mohapatra, P.K. and Khopkar, P.K. (1989) Hydrolysis of actinides and lanthanides hydrolysis of some trivalent actinide and lanthanide ions studied by extraction with thenoyltrifluoroacetone. Polyhedron, 16, 2071-2076. 

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