Trivalent lanthanide interactions with a terdentate bis(dialkyltriazinyl)pyridine ligand studied by electrospray ionization mass spectrometry

被引:79
作者
Colette, S
Amekraz, B [1 ]
Madic, C
Berthon, L
Cote, G
Moulin, C
机构
[1] CEA, DEN, DPC, SCPA,LAS2O, F-91191 Gif Sur Yvette, France
[2] CEA Saclay, DEN, SAC DIR, F-91191 Gif Sur Yvette, France
[3] CEA Valrho, DEN, DRCP, SCPS,LCSE, F-30207 Bagnols Sur Ceze, France
[4] ENSCP, UMR CNRS 7575, F-75231 Paris 05, France
关键词
D O I
10.1021/ic025894y
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridines (DATPs) belong to a new family of extracting agents recently developed in the framework of nuclear fuel reprocessing. These molecules exhibit exceptional properties to separate actinides(III) from lanthanides(III) in nitric acid solutions. A previous work showed that electrospray ionization mass spectrometry (ESI-MS) is a reliable technique to provide solution data such as stoichiometries and conditional stability constants of various DATP complexes with europium and evidenced the unusual capability of DiPTP [bis-(di-iso-propyltriazinyl)pyridine] ligand to form 1:3 complexes in nitric acid solution. This latter result is further investigated by considering DiPTP complexation features with the complete lanthanide family. As a starting point of the experimental procedure used for stability constant evaluation, the intensity distribution of ions detected by ESI-MS is studied for solutions containing Ln(NO3)(3) in water/methanol (1:1 v/v) with the pH value set at 2.8 and 4.6 by HNO3 additions. At pH 2.8, the nitrate anions are found to prevent lanthanides from processes occurring within the ion source: redox phenomena or gas-phase reactions with methanol which give species such as [Ln(MeO)(2)](+). Thus, the total intensity of MS signals from [Ln(NO3)(2)(H2O)(p)(MeOH)(n)](+) ions is found proportional to the metal ion concentration. At pH 4.6, with lower nitrate concentration, the nature of the species identified on mass spectra depends on the electronic properties of the lanthanide elements. It is shown that Ln(III) complexation with DiPTP leads to the exclusive formation of 1:3 complexes with the whole lanthanide series which may be due not only to the hydrophobic exterior of the ligand but also to the unusual electronic density distribution in DATP ligands as compared with other aza-aromatic ligands. The conditional stability constants of the 1:3 lanthanide(III) complexes with DiPTP have been determined at pH 2.8 and are found to increase almost regularly from La (log beta(3)(app) = 11.7 +/- 0.1) to Lu (109 beta(3)(app) = 16.7 +/- 0.8). Moreover, the kinetic stability of the gas-phase 1:3 complexes obtained by electrospray has been investigated by energy-resolved collision-induced dissociation and provides useful information on the bonding and structure.
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页码:2215 / 2226
页数:12
相关论文
共 58 条
[1]   ELECTROSPRAY MASS-SPECTROMETRY AS A TECHNIQUE FOR ELEMENTAL ANALYSIS - PRELIMINARY-RESULTS [J].
AGNES, GR ;
HORLICK, G .
APPLIED SPECTROSCOPY, 1992, 46 (03) :401-406
[2]  
[Anonymous], 1985, ION SOLVATION
[3]  
Berthet JC, 2002, EUR J INORG CHEM, P1439
[4]   1ST STUDIES OF THE GAS-PHASE ION CHEMISTRY OF M3+ METAL-ION LIGANDS [J].
BLADES, AT ;
JAYAWEERA, P ;
IKONOMOU, MG ;
KEBARLE, P .
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1990, 101 (2-3) :325-336
[5]   Americium(III) and europium(III) solvent extraction studies of amide-substituted triazine ligands and complexes formed with ytterbium(III) [J].
Boubals, N ;
Drew, MGB ;
Hill, C ;
Hudson, MJ ;
Iveson, PB ;
Madic, C ;
Russell, ML ;
Youngs, TGA .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (01) :55-62
[6]   Trivalent lanthanide ions:: versatile coordination centers with unique spectroscopic and magnetic properties [J].
Bünzli, JCG ;
André, N ;
Elhabiri, M ;
Muller, G ;
Piguet, C .
JOURNAL OF ALLOYS AND COMPOUNDS, 2000, 303 :66-74
[7]   POTENTIOMETRIC, CALORIMETRIC, AND SOLUTION NMR-STUDIES OF A TRIDENTATE LIGAND WHICH HAS A MARKED PREFERENCE FOR FORMATION OF BIS(LIGAND) VERSUS MONO(LIGAND) LANTHANIDE COMPLEXES AND WHICH EXHIBITS HIGH SELECTIVITY FOR HEAVIER LANTHANIDES [J].
CARAVAN, P ;
HEDLUND, T ;
LIU, S ;
SJOBERG, S ;
ORVIG, C .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (45) :11230-11238
[9]  
CHOPPIN GR, 1994, HANDB PHYSI, V18, P559
[10]   Use of electrospray mass spectrometry (ESI-MS) for the study of europium(III) complexation with bis(dialkyltriazinyl)pyridines and its implications in the design of new extracting agents [J].
Colette, S ;
Amekraz, B ;
Madic, C ;
Berthon, L ;
Cote, G ;
Moulin, C .
INORGANIC CHEMISTRY, 2002, 41 (26) :7031-7041