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Coordination of trivalent lanthanum and cerium, and tetravalent cerium and actinides (An = Th(IV), U(IV), Np(IV)) by a 4-phosphoryl 1H-pyrazol-5-olate ligand in solution and the solid state.
- Source :
-
Dalton Transactions: An International Journal of Inorganic Chemistry . 3/14/2021, Vol. 50 Issue 10, p3550-3558. 9p. - Publication Year :
- 2021
-
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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 50
- Issue :
- 10
- Database :
- Academic Search Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 149307359
- Full Text :
- https://doi.org/10.1039/d1dt00365h