X-ray absorption fine structures of uranyl(V) complexes in non-aqueous solutions

Actinide elements at oxidation states +5 and +6 exist as actinyl ions (AnO2n+, An = U, Np, Pu, Am) with typical trans-dioxo arrangement. Among them U(V) is quite instable due to the disproportionation. Recently, U(V) attracts special interest, because this field of actinides has been little explored despite its importance in the nuclear engineering. Especially, the U(V) solution chemistry is quite important in nuclear fuel reprocessing and environmental risks with long-term storage of radioactive waste. Structure of U(V) species is one of the essential parts of its chemistry. Actually, several crystal structures of U(V) compounds were reported previously. On the other hand, structure of U(V) species in solutions are not investigated so far except for EXAFS studies of UVO2(CO3)35– in an aqueous system.1,2 In this study, we report the structure determination of two U(V) complexes, [UVO2(salophen)DMSO]– (1V, salophen = N,N’-disalicylidene-o-phenylenediaminate) and [UVO2(dbm)2DMSO]– (2V, dbm = dibenzoylmethanate), in DMSO.3-6
The k3-weighted EXAFS spectra of 1V, 1VI, 2V, and 2VI and their Fourier transforms (FTs) are shown in Fig. 1. The structures of these U(V) and U(VI) complexes in DMSO solutions were determined by the EXAFS curve fits on the basis of the molecular structures of 1VI and 2VI from single crystal X-ray analyses.5,6 The best fit curve for each EXAFS spectrum and FTs are also displayed in Fig. 1. As a result, the interatomic distances between U and axial O (Oax) were determined as 1.84 Å for 1V and 1.85 Å for 2V, which are comparable with other U(V) complexes in crystal structures. On the other hand, the U–Oax distances of 1VI and 2VI are evaluated 1.80 and 1.78 Å, respectively. The lengthening of the U–Oax distance of 0.04–0.07 Å with the reduction of U(VI) to U(V) corroborates our previous estimation from IR spectra for 1V/1VI and 2V/2VI couples.4,5 The interatomic distances between U and coordinating atoms of salophen2– and dbm– are also lengthened 0.04–0.14 Å with the reduction from U(VI) to U(V). It should be noted that a long interatomic distance between U and O of DMSO (U–ODMSO; ca. 2.90 Å) was found in both 1V and 2V. Although these U–ODMSO distances seem unusual, those are still shorter than the sum of van der Waals radii of U and O (1.86 + 1.52 = 3.38 Å),9 indicating that such a long U–ODMSO interaction is still possible. The long U–ODMSO distance implies the very weak coordination of DMSO to U(V) in 1V and 2V. Actually, we previously observed that 1V may release DMSO at lower DMSO concentration.1 The week coordination of the unidentate ligand (L) such as DMSO might be a reason why U(V) solvates (UVO2(L)5+) is instable even in L,10,11 and provides an insight that strong multidentate ligand is required for stabilization of U(V).