Please use this identifier to cite or link to this item:
|Title:||Conformational and Coordination Equilibria on DOTA Complexes of Lanthanide Metal Ions in Aqueous Solution Studied by 1H-NMR Spectroscopy||Authors:||Aime, Silvio
Marques, M. Paula M.
Geraldes, Carlos F. G. C.
Merbach, André E.
|Issue Date:||7-May-1997||Publisher:||American Chemical Society||Citation:||Inorganic Chemistry. 36:10 (1997) 2059-2068||Abstract:||A 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)]-.||URI:||http://hdl.handle.net/10316/10318||ISSN:||0020-1669||DOI:||10.1021/ic961364o||Rights:||openAccess|
|Appears in Collections:||FCTUC Ciências da Vida - Artigos em Revistas Internacionais|
Show full item record
Files in This Item:
|Conformational and Coordination Equilibria on DOTA Complexes.pdf||223.8 kB||Adobe PDF||View/Open|
WEB OF SCIENCETM
checked on Sep 2, 2021
checked on Oct 8, 2021
checked on Oct 8, 2021
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.