Solvent-extraction chelating extractants, structural

The given structure shows two molecules of TTA to have reacted with a cobalt ion to form the cobalt-TTA complex, in which the cobalt atom forms a valence bond solid lines) with one, and a coordinate bond (broken lines) with the other, oxygen atom of each TTA molecule. Thus, in the cobalt-TTA complex there is a six-membered ring formed by each TTA molecule with the cobalt atom. Metal chelate complexes of this type have good stability, they are nonpolar and soluble in the organic phase. The usefulness of the chelating extractants in solvent extraction is therefore obvious. 

All these methods have found applications in theoretical considerations of numerous problems more or less directly related to solvent extraction. The MM calculated structures and strain energies of cobalt(III) amino acid complexes have been related to the experimental distribution of isomers, their thermodynamic stability, and some kinetic data connected with transition state energies [15]. The influence of steric strain upon chelate stability, the preference of metal ions for ligands forming five- and six-membered chelate rings, the conformational isomerism of macrocyclic ligands, and the size-match selectivity were analyzed [16] as well as the relation between ligand structures, coordination stereochemistry, and the thermodynamic properties of TM complexes [17]. 

Figure 6. The dimers formed by phosphorus(V) acids in non-polar solvents, (A) and the structurally related pseudo-chelates (B) formed on extraction of metal cations.

Diphosphazane dioxide complexes of lanthanides have potential application in the solvent extraction separation of lanthanides. Reaction of lanthanide nitrate with X2P(0)NPr )-P(0)X2(L-L) yields the bis chelate complexes Ln(NC>3)(L-L)2. The structure of the praseodymium complex has been determined by X-ray diffraction and the space group is P32- There are two independent molecules in the unit cell which differ in orientation of the phenyl group. The metal ion is ten-coordinated [264]. 

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