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NMR investigation of the lanthanide and actinide complexes of bis-triazine extracting agents
Desreux, Jean-François; Vidick, Geoffrey; Bouslimani, Nouri
2011In Valuenza, Fernando L.; Moyer, Bruce A. (Eds.) 19th International Solvent Extraction Conference
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Keywords :
NMR; extraction; BTP, BTBP
Abstract :
[en] Nuclear magnetic resonance spectroscopy (NMR) is applied to unravel the solution structure and the stoichiometry of the complexes formed between bis-triazine extracting agents (BTP and BTBP) and paramagnetic lanthanide ions. Highly rigid lanthanide perchlorate tris-complexes of threefold symmetry are formed by the pyridine bis-triazine BTP¿s while the bipyridine analogues (BTBP) form bis-complexes with a more open structure that leaves enough space for solvent molecules or anions. The nitrate ion is unable to enter the first coordination sphere of the tris-BTP complexes but the structure and stoichiometry of the bis-BTBP chelates are profoundly modified in presence of this ion. The NMR analysis is extended to actinides in various oxidation states despite technical difficulties. The NpO2+ ion is shown to form a 1:1 BTP complex in which the ligand is located in the plane perpendicular to the dioxo unit. No covalency contribution could be detected in the NMR spectra but such a contribution is clearly visible in the case of Am3+ and Cm3+. The latter induces very large paramagnetic shifts with a large contact contribution.
Disciplines :
Chemistry
Author, co-author :
Desreux, Jean-François ;  Université de Liège - ULiège > Département de chimie (sciences) > Département de chimie (sciences)
Vidick, Geoffrey ;  Université de Liège - ULiège > Centre de recherches du cyclotron
Bouslimani, Nouri;  Université de Liège - ULiège > Département de chimie
Language :
English
Title :
NMR investigation of the lanthanide and actinide complexes of bis-triazine extracting agents
Publication date :
07 October 2011
Event name :
19th International Solvent Extraction Conference
Event organizer :
Gecamin
Event place :
Santiago, Chile
Event date :
du 03 octobre 2011 au 07 octobre 2011
Audience :
International
Main work title :
19th International Solvent Extraction Conference
Editor :
Valuenza, Fernando L.
Moyer, Bruce A.
Pages :
133
Peer reviewed :
Peer reviewed
Available on ORBi :
since 14 February 2012

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