2,3-二羟基对苯二甲酰胺作为M(IV)螯合剂的表征

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

作者信息

Gramer Christine J, Raymond Kenneth N

机构信息

Chemical Sciences Division, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.

出版信息

Inorg Chem. 2004 Oct 4;43(20):6397-402. doi: 10.1021/ic0496267.

DOI:10.1021/ic0496267

PMID:15446889

Abstract

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)(-), Ce(ETAM)(4)(-), and Th(ETAM)(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[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 (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.

摘要

配体N,N'-二乙基-2,3-二羟基对苯二甲酰胺（ETAM）已被表征为锆（IV）、铈（IV）和钍（IV）的螯合剂。配合物[Zr(ETAM)₄]⁴⁻、[Ce(ETAM)₄]⁴⁻和[Th(ETAM)₄]⁴⁻的钾盐是在含有H₂ETAM、相应的M(acac)₄和4当量KOH的甲醇溶液中制备的。报道了K₄[Zr(ETAM)₄]（空间群C2/c，Z = 8，a = 27.576(3) Å，b = 29.345(3) Å，c = 15.266(2) Å，α = 90°，β = 118.688(4)°，γ = 90°）、[Me₃BnN]₄[Th(ETAM)₄]（空间群P，Z = 2，a = 13.7570(3) Å，b = 13.9293(3) Å，c = 26.9124(6) Å，α = 99.941(1)°，β = 94.972(1)°，γ = 103.160(1)°）和二聚体(NMe₄)₄[Th(ETAM)₃MeOH]₂（空间群P2₁/c，Z = 4，a = 18.2603(9) Å，b = 18.5002(9) Å，c = 19.675(1) Å，β = 117.298(1)°）的单晶X射线衍射分析结果。溶液热力学研究用于确定钍（IV）-ETAM的形成常数（log Kf和标准偏差）：log K₁₁₀ = 17.47(1)，log K₁₂₀ = 13.23(1)，log K₁₃₀ = 8.28(3)，log K₁₄₀ = 6.57(6)，以及log β₁₄₀ = 45.54(5)。这些结果支持了对苯二甲酰胺是锕系（IV）离子的高亲和力螯合剂这一假设，因此是用于核废料修复的有前景的配体这一观点。