Activation energies of intermolecular dynamics in ethylenediaminetetraacetate complexes with lanthanides: An effect of the "gadolinium break"

Activation energies of intermolecular dynamics in ethylenediaminetetraacetate complexes with lanthanides: An effect of the "gadolinium break" Full article

Journal

Inorganica Chimica Acta
ISSN: 0020-1693 , E-ISSN: 1873-3255

Output data

Year: 2016, Volume: 439, Pages: 117-122 Pages count : 6 DOI: 10.1016/j.ica.2015.10.009

Tags

Lanthanide complexes; EDTA; Lanthanide-induced shifts in NMR spectra; Kinetics of chemical exchange; Dynamic NMR; Aqueous solutions

Authors

Babailov Sergey P. ^1,2 , Chuikov Igor P. ³ , Kruppa Alexander I. ⁴

Affiliations

1	(Данные Web of science) Russian Acad Sci, AV Nikolaev Inst Inorgan Chem, Siberian Branch, Novosibirsk 630090, Russia
2	(Данные Web of science) Natl Res Tomsk Polytech Univ, Tomsk 634050, Russia
3	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, Voevodsky Inst Chem Kinet & Combust, Novosibirsk 630090, Russia

Earlier the monotonic increase of the free energy of chemical exchange processes along the series of lanthanide [Ln(H2O)(n)(EDTA(4))] complexes was found [Babailov S.P., Magnet. Reson. Chem., 2012, 50, 12, 793] for the yttrium subgroup (Tb3+, Ho3+, Tm3+, Yb3+ and Lu3+). In the present paper H-1 NMR measurements are reported for the aqueous solutions of [Ln(H2O)(n)(EDTA(4))] complexes of the cerium subgroup {La3+ (I), Pr3+ (II) and Eu3+ (III); n = 1, 2 and 3}. It is determined that the activation free energies (Delta G(298)(double dagger)) of the intermolecular EDTA(4) ions exchange at [Ln(H2O)(n)(EDTA(4))] complexes are 65 +/- 3, 65 +/- 3 and 64 +/- 3 kJ/mol for I, II and III respectively (at pD = 2.5). Comparison Delta G(298)(double dagger) values for the light and the heavy lanthanides showed a "gadolinium break" of the dependence of the Delta G(298)(double dagger) on the lanthanide cation numbers. The obtained results indicate that coordination compounds II and III may be considered as thermometric NMR sensor and lanthanide paramagnetic probes for in situ temperature control in solution. (C) 2015 Elsevier B.V. All rights reserved.

Babailov S.P. , Chuikov I.P. , Kruppa A.I.
Activation energies of intermolecular dynamics in ethylenediaminetetraacetate complexes with lanthanides: An effect of the "gadolinium break"
Inorganica Chimica Acta. 2016. V.439. P.117-122. DOI: 10.1016/j.ica.2015.10.009 WOS Scopus РИНЦ

Published print:

Jan 1, 2016

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