Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations

In order to investigate the relative effects of the differences between the structures and lipophilicities of 1,10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TA-18-crown-6) and the tetrabenzyl derivative of 1,10-dioxa-4, 7, 13, 16-tetraazacyclooctadecane (TBTA-18-crown-6) on their extraction-abilities and -selectivities for transition metal cations, constants of the overall extraction (logK(ex)) of 1: 1 (M: L) complexes, the distribution (K-D) for two diluents (CH2Cl2 and CHCl3) with different dielectric constants have been determined at 25 +/- 0.1 degreesC. The magnitude of logK(ex) is largely determined by that of K-D. The equilibrium constants of TA-18-crown-6 have been compared with those of TBTA-18-crown-6. It is found that: (i) logK(ex) sequences of TA-18-crown-6 and TBTA-18-crown-6 for transition metals in CH2Cl2 lie in order: Fe3+ > Cu2+ > Mn2+ > Co2+ > Cd2+ > Ni2+ > Zn2+ and Fe3+ > Cu2+ > Co2+ > Mn2+ > Ni2+ > Cd2+ > Zn2+ respectively; ( ii) the stability sequences of two types of tetra-aza-crown ethers with the transition metal cations in CHCl3 are the same as follows: Fe3+ > Ni2+ > Cu2+ > Co2+ > Zn2+ > Cd2+ > Mn2+, and (iii) unusual selectivities are observed for transition metal-tetra-aza-crowns, e.g. the high Fe3+/Mn+ selectivity factors (S-f) of TA-18-crown-6, except for the competitive-extractions for the special case in CHCl3 of TBTA-18-crown-6, it was found that the Mn2+/Mn+ values were relatively higher according to the other transition metal cations. A systematic sequence in these two types of solvents is not found for a given transition metal cation in terms of the variation of selectivity with the tetra-aza-crown ethers. The results provide alternatives for the rational design of other specific ligands on the transition metal cations.