Página 7 dos resultados de 7330 itens digitais encontrados em 0.010 segundos
Resultados filtrados por Publicador: American Chemical Society

Multinuclear magnetic resonance study of the structure and dynamics of lanthanide(III) complexes of the bis(propylamide) of diethylenetriaminepentaacetic acid in aqueous solution

Geraldes, Carlos F. G. C.; Urbano, Ana M.; Hoefnagel, Mattheus A.; Peters, Joop A.
Fonte: American Chemical Society Publicador: American Chemical Society
Tipo: Artigo de Revista Científica
Relevância na Pesquisa
The structure and dynamics of the lanthanide(II1) complexes of the bis(propy1amide) of diethylenetriaminepentaacetate (DTPA-PA3 in aqueous solution have been investigated by I3C and I7O NMR. With the use of the longitudinal 13C relaxation times of the NdlI1 complex it is shown that the organic ligand is bound to the lanthanide(II1) ion in an octadentate fashion via the three nitrogens of the diethylenetriamine backbone, the three carboxylate groups, and the two amide oxygens. I7O NMR measurements show that the coordination sphere is completed by one water ligand. The inversion of the lanthanide-bound nitrogens is precluded, and therefore four diastereomeric pairs of isomers are possible for these complexes. Low-temperature I3C NMR spectra show that all these isomers occur in solution. Three dynamic processes have been identified by means of variable-temperature NMR measurements: (i) rapid rotations of the carboxylate groups, (ii) racemization at the middle N atom via interconversions between the two possible conformations of the ethylene bridges, and (iii) racemization at the terminal N atoms of the diethylenetriamine backbone via decoordination-inversion-cmrdination. The barriers of the interconversions between the enantiomers have been determined by line-shape analysis and from coalescence temperatures. A comparison is made with the LnlI1 diethylenetriaminepentaacetate (DTPA) complexes.; http://dx.doi.org/10.1021/ic00063a037