The uranyl aryloxide, [UO(2)(OAr)(2)(THF)(2)], and uranyl chloride, [UO(2)Cl(2)(THF)(3)] or [UO(2)Cl(2)(THF)(2)](2) act as pre-catalysts for the ring opening polymerization of propylene oxide and cyclohexene oxide. Coordination of the monomers has been investigated using (1)H EXSY spectroscopy and kinetic and thermodynamic parameters reported. NMR analyses of the polymers suggest a bimetallic mechanism for the polymerization.

A comprehensive computational study on the ring-opening polymerization of propylene oxide catalyzed by uranyl chloride [UO(2)Cl(2)(THF)(3)] and the uranyl aryloxide [UO(2)(OAr)(2)(THF)(2)] (Ar = 2,6-(t)Bu(2)C(6)H(3)) is reported. The initiation and propagation steps have been probed and significant differences between the two catalysts discovered. The initiation step involving uranyl chloride is an intermolecular process because the orientation of the lone pair on the initiating chloride nucleophile is optimally oriented toward the empty σ*-antibonding orbital of the epoxide, which lowers the activation barrier by 22 kcal mol(-1). Thus, initiation is orbitally controlled. Propagation occurs through a dimeric species, and low-temperature fluorescence spectroscopy has been used to probe this experimentally. In contrast the initiation step for the uranyl aryloxide catalyzed mechanism is intramolecular because of the steric constraints imposed by the bulky substituents on the aryl ring and the fact that the lone pair on the nucleophile is able to approach the propylene oxide coordinated to the same uranium center. Thus, initiation is principally sterically controlled. Propagation is, however, intermolecular, and this can be traced to steric effects. Experimental evidence in the form of fluorescence spectroscopy and diffusion NMR has been used to explore the propagation process in solution.

The uranyl aryloxide [UO2(OAr)2(THF)2] (Ar = 2,6-(t)Bu2-C6H2) is an active catalyst for the ring-opening cyclo-oligomerization of ε-caprolactone and δ-valerolactone but not for β-butyrolactone, γ-butyrolactone, and rac-lactide. (1)H EXSY measurements give the thermodynamic parameters for exchange of monomer and coordinated THF, and rates of polymerization have been determined. A comprehensive theoretical examination of the mechanism is discussed. From both experiment and theory, the initiation step is intramolecular and in keeping with the accepted mechanism, while computational studies indicate that propagation can go via an intermolecular pathway, which is the first time this has been observed. The lack of polymerization for the inactive monomers has been investigated theoretically and C-H···π interactions stabilize the coordination of the less rigid monomers.

The unusual uranyl peroxide studtite, [UO(2)(η(2)-O(2))(H(2)O)(2)]·2H(2)O, is a phase alteration product of spent nuclear fuel and has been characterized by solid-state cyclic voltammetry. The voltammogram exhibits two reduction waves that have been assigned to the U(VI/V) redox couple at -0.74 V and to the U(V/IV) redox couple at -1.10 V. This potential shows some dependence upon the identity of the cation of the supporting electrolyte, where cations with larger ionic radii exhibit more cathodic reduction potentials. Raman spectroelectrochemistry indicated that exhaustive reduction at either potential result in a product that does not contain peroxide linkers and is likely to be UO(2). On the basis of the reduction potentials, the unusual behavior of neptunium in the presence of studtite can be rationalized. Furthermore, the oxidation of other species relevant to the long-term storage of nuclear fuel, namely, iodine and iodide, has been explored. The phase altered product should therefore be considered as electrochemically noninnocent. Radiotracer studies with (241)Am show that it does not interact with studtite so mobility will not be retarded in repositories. Finally, a large difference in band gap energies between studtite and its dehydrated congener metastudtite has been determined from the electronic absorption spectra.

The solid-sate structures of the two uranyl peroxides studtite, [UO2(η(2)-O2)(H2O)2]·2H2O, and metastudtite [UO2(η(2)-O2)(H2O)2] have been determined by U-L3 edge extended X-ray absorption fine structure (EXAFS) spectroscopy and show that upon removal of the interstitial water in studtite there are structural changes with a small shortening of the U-O(peroxo) and small lengthening of the U-O(yl) bonds. High-energy resolution X-Ray absorption near edge structure (HR-XANES) spectroscopy has been used to probe the differences in the local electronic structure and, supported by ab initio FEFF9.5.1 calculations, dehydration causes a shift to higher energies of the occupied O p-DOS and U d- and f-DOS of metastudtite. The HR-XANES spectrum of schoepite, [(UO2)4O(OH)6]·6H2O, has been measured as the White Line intensity can give information on the mixing of metal and ligand atomic orbitals. There is an indication for higher degree of ionicity for the U-OH bond in schoepite compared to the U-O2 bond in studtite.