Issue 21, 2010
From the journal:

Dalton Transactions

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)†

Frank W. Lewis,*a   Laurence M. Harwood,*a   Michael J. Hudson,a   Michael G. B. Drew,a   Giuseppe Modolo,b   Michal Sypula,b   Jean F. Desreux,c   Nouri Bouslimanic  and  Geoffrey Vidickc  

* Corresponding authors

a Department of Chemistry, The University of Reading, Whiteknights, Reading, UK
E-mail: f.lewis@reading.ac.uk, l.m.harwood@reading.ac.uk
Fax: +44 (0) 118 378 6121
Tel: +44 (0) 118 378 7417

b Forschungszentrum Jülich GmbH, Sicherheitsforschung und Reaktortechnik, D-52425 Jülich, Germany
E-mail: g.modolo@fz-juelich.de
Tel: + 492 46161 4896

c Coordination and Radiochemistry, University of Liège, Sart Tilman B16, B-4000 Liège, Belgium
E-mail: jf.desreux@ulg.ac.be
Fax: + 324 366 4739
Tel: + 324 366 3501

Abstract

The new ligand 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 n-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. The metal(III) cations are extracted as the 1 : 1 complex from nitric acid. 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.

Graphical abstract: 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)

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Article information

DOI
https://doi.org/10.1039/B924988E
Article type
Paper
Submitted
27 Nov 2009
Accepted
26 Mar 2010
First published
23 Apr 2010

Dalton Trans., 2010,39, 5172-5182

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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)

F. W. Lewis, L. M. Harwood, M. J. Hudson, M. G. B. Drew, G. Modolo, M. Sypula, J. F. Desreux, N. Bouslimani and G. Vidick, Dalton Trans., 2010, 39, 5172 DOI: 10.1039/B924988E

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