Lanthanide complexes of polyoxometalates: characterization by tungsten-183 and phosphorus-31 nuclear magnetic resonance spectroscopy

Abstract

Lanthanide complexes of three classes of polyoxoanions have been characterized by multinuclear (¹⁸³W and ³¹P) NMR spectroscopy among other techniques. The tetrabutylammonium salt of the lacunary [α-2-P₂W₁₇O₆₁]^10- , prepared by metathesis of the potassium salt, was isomerically pure according to ¹⁸³W and ³¹P NMR spectroscopy. The K₁₃[Ln(SiW₁₁O₃₉)₂] family of complexes show a six-line pattern in the ¹⁸³W NMR spectrum at 40 °C for the lanthanum derivative, consistent with a symmetrical structure (C_2h or C_2v symmetry), and eleven-line patterns for the ytterbium and lutetium analogues at 23 °C, suggesting a lower symmetry (C₂) for complexes of the heavier lanthanide ions. The same phenomenon was observed for the [α-2-Ln(P₂W₁₇O₆₁)₂] ^17- family of compounds. High-temperature ¹⁸³W NMR experiments on the [Lu(SiW₁₁O₃₉)₂]^13- and the [α-2-Lu(P₂W₁₇O₆₁)₂] ^17- compounds showed a reversible broadening and coalescence of the resonances, due to a dynamic effect, possibly rotation of the oxoanion ligands.

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