Characterization of 2,3-dihydroxyterephthalamides as M(IV) chelators.

The ligand N,N'-diethyl-2,3-dihydroxyterephthalamide (ETAM) has been characterized as a chelator for Zr(IV), Ce(IV), and Th(IV). The K(+) salts of the complexes [Zr(ETAM)(4)](4)(-), [Ce(ETAM)(4)](4)(-), and [Th(ETAM)(4)](4)(-) were prepared in a MeOH solution containing H(2)ETAM, the corresponding M(acac)(4), and 4 equiv of KOH. Single-crystal X-ray diffraction analyses are reported for K(4)[Zr(ETAM)(4)] (C2/c, Z = 8, a = 27.576(3) A, b = 29.345(3) A, c = 15.266(2) A, alpha = 90 degrees, beta = 118.688(4) degrees, gamma = 90 degrees ), [Me(3)BnN](4)[Th(ETAM)(4)] (P, Z = 2, a = 13.7570(3) A, b = 13.9293(3) A, c = 26.9124(6) A, alpha = 99.941(1) degrees, beta = 94.972(1) degrees, gamma = 103.160(1) degrees ), and the dimeric (NMe(4))(4)[Th(ETAM)(3)MeOH](2) (P2(1)/c, Z = 4, a = 18.2603(9) A, b = 18.5002(9) A, c = 19.675(1) A, beta = 117.298(1) degrees ). Solution thermodynamic studies were used to determine formation constants (log K(f) and esd) for Th(IV)-ETAM log K(110) =17.47(1), log K(120) = 13.23(1), log K(130) = 8.28(3), log K(140) = 6.57(6), and log beta(140) = 45.54(5). These results support the hypothesis that the terephthalamides are high-affinity chelators for the actinide(IV) ions and thus promising ligands for use in nuclear waste remediation.