Coordination of trivalent lanthanum and cerium, and tetravalent cerium and actinides (An = Th(<scp>iv</scp>), U(<scp>iv</scp>), Np(<scp>iv</scp>)) by a 4-phosphoryl 1<i>H</i>-pyrazol-5-olate ligand in solution and the solid state

Abstract

Structural investigations of three actinide(iv) 4-phosphoryl 1H-pyrazol-5-olate complexes (An = Th(iv), U(iv), Np(iv)) and their cerium(iv) analogue display the same metal coordination in the solid state. The mononuclear complexes show the metal centre in a square antiprismatic coordination geometry composed by the two O-donor atoms of four deprotonated ligands. Detailed solid state analysis of the U(iv) complex shows that dependent on the solvent used altered arrangements are observable, resulting in a change in the coordination polyhedron of the U(iv) metal centre to bi-capped trigonal prismatic. Further, single crystal analyses of the La(iii) and Ce(iii) complexes show that the ligand can also act as a neutral ligand by protonation of the pyrazolyl moiety. All complexes were comprehensively characterized by NMR, IR and Raman spectroscopy. A single resonance in each of the 31P NMR spectra for the La(iii), Ce(iii), Ce(iv), Th(iv) and Np(iv) complex indicates the formation of highly symmetric complex species in solution. Extended X-ray absorption fine structure (EXAFS) investigations provide evidence for the same local structure of the U(iv) and Np(iv) complex in toluene solution, confirming the observations made in the solid state.

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