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Issue 9, 2013
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Exploring the solution behavior of f-element coordination compounds: a case study on some trivalent rare earth and plutonium complexes

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Abstract

Several rare earth coordination compounds and the first actinide coordination compound of the recently introduced multifunctional ligand (S)P[N(Me)N[double bond, length as m-dash]C(H)Py]3 (1, Py = pyridyl) have been synthesized and characterized. The electronic and structural properties of these complexes were probed by X-ray diffraction analysis, X-ray absorption fine structure (XAFS), and advanced nuclear magnetic resonance (NMR) spectroscopy. Pulsed field-gradient spin-echo (PGSE) diffusion measurements and 1H,19F heteronuclear Overhauser spectroscopy (HOESY) revealed that the degree of ion pairing of the trivalent rare earth complexes [Ln(1)(OTf)3] (Ln = Y (2), La (3), Sm (4), and Lu (5); [OTf] = [O3SCF3]) depends on their metal cation ionic radii and decreases in acetonitrile solution for the smaller lanthanides. The plutonium(III) complex 6 exhibits, however, a significantly different behavior in solution and has a much stronger tendency to form solvent-separated ion pairs.

Graphical abstract: Exploring the solution behavior of f-element coordination compounds: a case study on some trivalent rare earth and plutonium complexes

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Publication details

The article was received on 14 Mar 2013, accepted on 14 May 2013 and first published on 30 May 2013


Article type: Edge Article
DOI: 10.1039/C3SC50708D
Citation: Chem. Sci., 2013,4, 3717-3724
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    Exploring the solution behavior of f-element coordination compounds: a case study on some trivalent rare earth and plutonium complexes

    M. W. Löble, P. Oña-Burgos, I. Fernández, C. Apostolidis, A. Morgenstern, O. Walter, F. Bruchertseifer, P. Kaden, T. Vitova, J. Rothe, K. Dardenne, N. L. Banik, A. Geist, M. A. Denecke and F. Breher, Chem. Sci., 2013, 4, 3717
    DOI: 10.1039/C3SC50708D

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