Please use this identifier to cite or link to this item:
DC FieldValueLanguage
dc.contributor.authorAime, Silvio-
dc.contributor.authorBotta, Mauro-
dc.contributor.authorFasano, Mauro-
dc.contributor.authorMarques, M. Paula M.-
dc.contributor.authorGeraldes, Carlos F. G. C.-
dc.contributor.authorPubanz, Dirk-
dc.contributor.authorMerbach, André E.-
dc.identifier.citationInorganic Chemistry. 36:10 (1997) 2059-2068en_US
dc.description.abstractA variable-temperature, -pressure, and -ionic strength 1H NMR study of the DOTA complexes of different trivalent cations (Sc, Y, La, Ce → Lu) (DOTA = 1,4,7,10-tetraaza-1,4,7,10-tetrakis(carboxymethyl)cyclododecane) yielded data that are in contradiction with the hitherto used model of only two enantiomeric pairs of diastereoisomers that differ in the ligand conformations. A two-isomer equilibrium cannot explain the newly observed apparent reversal of the isomer ratio at the end of the series. As both conformers may lose their inner sphere water molecule, a coordination equilibrium may be superimposed on this conformational equilibrium, as shown by large positive reaction volumes for the isomerization of [Ln(DOTA)(H2O)x]- (Ln = Yb, Lu; x = 1, 0). The isomerization of [Nd(DOTA)(H2O)]- and [Eu(DOTA)(H2O)]- is purely conformational, as shown by near-zero reaction volumes. The measured isomerization enthalpies and entropies agree with this model. The shift of the isomerization equilibria by a variety of non-coordinative salts depends on the ligand conformation rather than the presence or absence of the inner sphere water molecule. This results from weak ion binding and water solvent stabilization of one ligand conformation, rather than the decrease of the activity of the bulk water in the solution, as shown by UV−vis measurements of the coordination number sensitive transition 5F0 → 7D0 of Eu(III) as a function of ionic strength. Fluoride ions replace a water molecule in the inner coordination sphere, preferentially for one of the conformational isomers, as proven by 19F-NMR shifts and the appearance of a third set of resonances corresponding to [Eu(DOTA)F]2- in the 1H-NMR spectrum of [Eu(DOTA)(H2O)]-.en_US
dc.publisherAmerican Chemical Societyen_US
dc.titleConformational and Coordination Equilibria on DOTA Complexes of Lanthanide Metal Ions in Aqueous Solution Studied by 1H-NMR Spectroscopyen_US
item.fulltextCom Texto completo-
item.grantfulltextopen- de Ciências e Tecnologia, Universidade de Coimbra- de Coimbra- Chemistry Center-
Appears in Collections:FCTUC Ciências da Vida - Artigos em Revistas Internacionais
Files in This Item:
File Description SizeFormat
Conformational and Coordination Equilibria on DOTA Complexes.pdf223.8 kBAdobe PDFView/Open
Show simple item record


checked on May 29, 2020

Page view(s)

checked on Jul 8, 2020


checked on Jul 8, 2020

Google ScholarTM




Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.