Crystallographic, X-ray absorption, and IR studies of solid- and solution-state structures of tris(nitrato) N,N,N′,N′-tetraethylmalonamide complexes of lanthanides.: Comparison with the americium complex

被引:45
作者
Den Auwer, C [1 ]
Charbonnel, MC
Drew, MGB
Grigoriev, M
Hudson, MJ
Iveson, PB
Madic, C
Nierlich, M
Presson, MT
Revel, R
Russell, ML
Thuéry, P
机构
[1] CEA Marcoule, DCC, DRRV, SEMP,Lab Chim Theor & Struct, F-30207 Bagnols Sur Ceze, France
[2] Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England
[3] Russian Acad Sci, Inst Phys Chem, Moscow, Russia
[4] CEA Saclay, CNRS URA 331, DSM, DRECAM,SCM, F-91191 Gif Sur Yvette, France
关键词
D O I
10.1021/ic990817x
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
To fine-tune the design of optimized donor ligands for nuclear waste actinide selective extraction, both electronic and molecular structures of the actinide complexes that are formed must be investigated. In particular, to achieve the selective complexation of transplutonium 3+ ions versus lanthanide 3+ ions is one of the major challenges, given the chemical similarities between these two f-element families. In this work, the structure of solvent-phase M(NO3)(3)(TEMA)(2) complexes (Ln = Nd, Eu, Ho, Yb, Lu, Am; TEMA = N,N,N',N'-tetraethylmalonamide) was investigated by liquid-phase spectroscopic methods among which extended X-ray absorption fine structure played a major role. In addition, the crystal structures of the species Nd(NO3)(3)(TEMA)(2) and Yb(NO3)(3)(TEMA)(2) have been determined by X-ray diffraction. Nd(NO3)(3)(C11N2O2H22)(2) crystallizes in the monoclinic system (P2(1) space group; a = 11.2627(4) Angstrom, b = 20.5992(8) Angstrom, c = 22.2126(8) Angstrom; alpha = gamma = 90 degrees, beta = 102.572(1)degrees; Z = 6), and Yb(NO3)(3)(C11N2O2H22)(2) crystallizes in the orthorhombic system (P2(1)2(1)2(1) space group; a = 9.3542(1) Angstrom, b = = 18.1148(2) Angstrom, c = 19.7675(2) Angstrom; alpha = beta = gamma = 90 degrees; Z = 4). In the solvent phase, the metal polyhedron was found to be similar to that of the solid-state complex Nd(NO3)(3)(TEMA)(2) for M = Nd to Ho. For M = Yb and Lu, a significant elongation of one nitrate oxygen bond was observed. Comparison with measurements on the Am(NO3)(3)(TEMA)(2) complex in ethanol has shown the similarities between the Nd3+ and Am3+ coordination spheres.
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页码:1487 / 1495
页数:9
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