Article (Scientific journals)
Interaction of 6,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2:6,2-terpyridine (CyMe4-BTTP) with some trivalent ions such as lanthanide(III) ions and americium(III)
Lewis, Frank; Harwood, Laurance; Hudson, Michael J. et al.
2010In Dalton Transactions, 39, p. 5172-5182
Peer reviewed
 

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Keywords :
actinides; extraction; lanthanides; nuclear magnetic resonance; triazine; paramagnetic
Abstract :
[en] The new solvent extraction reagent 6,6’’-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2’:6’,2’’-terpyridine (CyMe4-BTTP) has been synthesized in 4 steps from 2,2’:6’,2’’-terpyridine. Detailed NMR and mass spectrometry studies indicate that the ligand forms 1:2 complexes with lanthanide(III) perchlorates where the aliphatic rings are conformationally constrained whereas 1:1 complexes are formed with lanthanide(III) nitrates where the rings are conformationally mobile. An optimized structure of the 1:2 solution complex with Yb(III) was obtained from the relative magnitude of the induced paramagnetic shifts. X-ray crystallographic structures of the ligand and of its 1:1 complex with Y(III) were also obtained. The NMR and mass spectra of [Pd(CyMe4-BTTP)]n2n+ are consistent with a dinuclear double helical structure (n = 2). In the absence of a phase-modifier, CyMe4-BTTP in 1-octanol showed a maximum distribution coefficient of Am(III) of 0.039 (±20%) and a maximum separation factor of Am(III) over Eu(III) of 12.0 from nitric acid. From nitric acid, the metal(III) cations are extracted as the 1:1 complex. The generally low distribution coefficients observed compared with the BTBPs arise because the 1:1 complex of CyMe4-BTTP is considerably less hydrophobic than the 1:2 complexes formed by the BTBPs. In M(BTTP)3+ complexes, there is a competition between the nitrate ions and the ligand for the complexation of the metal.
Disciplines :
Chemistry
Author, co-author :
Lewis, Frank;  The University of Reading, Whiteknights, Reading, UK RG6 6AD > Department of Chemistry
Harwood, Laurance;  The University of Reading, Whiteknights, Reading, UK RG6 6AD > Department of Chemistry
Hudson, Michael J.;  The University of Reading, Whiteknights, Reading, UK RG6 6AD > Department of Chemistry
Drew, Michael G. B.;  The University of Reading, Whiteknights, Reading, UK RG6 6AD > Department of Chemistry
Modolo, Giuseppe;  Forschungszentrum Jülich GmbH, Sicherheitsforschung und Reaktortechnik, D-52425 Jülich, Germany
Sypula, Michal;  Forschungszentrum Jülich GmbH, Sicherheitsforschung und Reaktortechnik, D-52425 Jülich, Germany
Desreux, Jean-François ;  Université de Liège - ULiège > Département de chimie (sciences) > Chimie de coordination et radiochimie
Bouslimani, Nouri ;  Université de Liège - ULiège > Département de chimie (sciences) > Chimie de coordination et radiochimie
Vidick, Geoffrey ;  Université de Liège - ULiège > Département de chimie (sciences) > Chimie de coordination et radiochimie
Language :
English
Title :
Interaction of 6,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2:6,2-terpyridine (CyMe4-BTTP) with some trivalent ions such as lanthanide(III) ions and americium(III)
Publication date :
2010
Journal title :
Dalton Transactions
ISSN :
1477-9226
eISSN :
1477-9234
Publisher :
Royal Society of Chemistry (RSC), Cambridge, United Kingdom
Volume :
39
Pages :
5172-5182
Peer reviewed :
Peer reviewed
Name of the research project :
ACSEPT
Available on ORBi :
since 21 May 2010

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