Reference : Interaction of 6,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/38433
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)
English
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 mailto [Université de Liège - ULg > Département de chimie (sciences) > Chimie de coordination et radiochimie > >]
Bouslimani, Nouri [Université de Liège - ULg > Département de chimie (sciences) > Chimie de coordination et radiochimie >]
Vidick, Geoffrey mailto [Université de Liège - ULg > Département de chimie (sciences) > Chimie de coordination et radiochimie >]
2010
Dalton Transactions
39
5172-5182
Yes
International
[en] actinides ; extraction ; lanthanides ; nuclear magnetic resonance ; triazine ; paramagnetic
[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.
ACSEPT
http://hdl.handle.net/2268/38433

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