Issue 16, 2002
From the journal:

Journal of the Chemical Society, Dalton Transactions

The affinity and selectivity of terdentate nitrogenligands towards trivalent lanthanide and uranium ions viewed from the crystal structures of the 1 ∶ 3 complexes

Jean-Claude Berthet,*a   Yannick Miquel,a   Peter B. Iveson,a   Martine Nierlich,b   Pierre Thuéry,b   Charles Madicc  and  Michel Ephritikhine*a  

* Corresponding authors

a Laboratoire de Chimie de Coordination, Service de Chimie Moléculaire, DSM, DRECAM, CNRS URA 331, CEA/Saclay, 91191 Gif-sur-Yvette, France
E-mail: ephri@drecam.cea.fr

b Laboratoire de Cristallochimie, Service de Chimie Moléculaire, DSM, DRECAM, CNRS URA 331, CEA/Saclay, 91191 Gif-sur-Yvette, France

c DEN, CEA/Saclay, 91191 Gif-sur-Yvette, France

Abstract

Treatment of LnI3 (Ln = La, Ce) or [UI3(py)4] with 3 equivalents of terpy in acetonitrile gave the tris(terpy) complexes [M(terpy)3]I3. Addition of 3 equivalents of Rbtp (2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine) to MX3 (X = I or OSO2CF3) in pyridine or acetonitrile afforded the tris(Rbtp) compounds [M(Rbtp)3]X3. By comparison with terpy, the Rbtp ligand has a better affinity for the 4f and 5f ions and is more selective for U(III) than for Ce(III) or La(III). This trend has been revealed by 1H NMR competition experiments and X-ray crystallographic studies which show that in the [M(terpy)3]3+ and [M(Rbtp)3]3+ cations, the M–N(Rbtp) bond lengths are shorter than the M–N(terpy) bond lengths, and the U–N bond lengths are shorter than the corresponding Ce–N or La–N bond distances.

Graphical abstract: The affinity and selectivity of terdentate nitrogen ligands towards trivalent lanthanide and uranium ions viewed from the crystal structures of the 1 ∶ 3 complexes

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Article information

DOI
https://doi.org/10.1039/B203725D
Article type
Paper
Submitted
17 Apr 2002
Accepted
13 Jun 2002
First published
23 Jul 2002

J. Chem. Soc., Dalton Trans., 2002, 3265-3272

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The affinity and selectivity of terdentate nitrogen ligands towards trivalent lanthanide and uranium ions viewed from the crystal structures of the 1 ∶ 3 complexes

J. Berthet, Y. Miquel, P. B. Iveson, M. Nierlich, P. Thuéry, C. Madic and M. Ephritikhine, J. Chem. Soc., Dalton Trans., 2002, 3265 DOI: 10.1039/B203725D

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