Structural and Bonding Analysis in Monomeric Actinide(IV) Oxalate from Th(IV) to Pu(IV): Comparison with the An(IV) Nitrate Series
Christelle Tamain, Matthieu Autillo, Dominique Guillaumont, Laetitia Guérin, Richard E. Wilson, Claude Berthon
Abstract
Single-crystal X-ray diffraction (SC-XRD) structures and Raman spectra of a series of new isomorphous molecular An(IV)-oxalate compounds (Th, U, Np, and Pu) are reported. These complexes are crystallized with cobalt(III) hexamine ([Co(NH3)6]3+) as the counter cations, [Co(NH3)6]2[An(C2O4)5]·4H2O, revealing five bidentate nonbridging oxalate ligands in the first coordination sphere (CN = 10). The nonbridging oxalate is rather uncommon for An(IV)-oxalate systems, which are widely characterized as polymeric compounds. Density functional theory (DFT) calculations were performed to examine the bonding between An(IV) cations and oxalate ligands. For comparison, we also report results obtained for the An(IV)-hexanitrate series, [(C2H5)4N]2[An(NO3)6] (with An = Th, U, Np, Pu, and Ce), which consists of O-donor ligands as well but with a larger coordination number (CN = 12). The bonding analysis confirms that the actinide–oxygen bond is predominantly ionic with a minor increase in covalency from Th to U and slight variations from U to Pu. Further comparison showed that the charge transfer increases slightly when increasing the number of anions in the coordination sphere (C2O42–: CN = 10; NO3–: CN = 12), but covalent effects as indicated by the amount of internuclear electron density accumulation are small and similar for oxalate and nitrate.