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

Chemical Science Pub Date: 2013-05-30 DOI: 10.1039/C3SC50708D

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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