Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes

Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes

“…[1][2][3][4][5][6] In the case of metal-metal bonds, those involving actinides are fundamentally different from their transition metal and lanthanide counterparts as a result of f orbital participation in bonding, coordinative diversity, and access to a wide range of oxidation states. Understanding these fundamental properties is of importance in nuclear fuel reprocessing, where small differences in covalency between the 4 and 5f elements may provide opportunities to improve separations.…”

A Structural and Spectroscopic Study of the First Uranyl Selenocyanate, [Et4N]3[UO2(NCSe)5]

“…A further interesting photophysical property of certain uranyl compounds are thermochromic effects. Thus the compound [C 4 mim] 3 [UO 2 (NCS) 5 ] (C 4 mim = 1-butyl-3-methylimidazolium) is thermochromic in ionic liquids [10] but in organic solvents [Et 4 N] 3 [UO 2 (NCS) 5 ] is not [11]. We have reported on the latter compound recently and now extend our study to the selenocyanate [ …”

“…A yellow precipitate was formed which was soluble in dichloromethane or acetone. We have noted that whilst this compound is air and moisture stable, it is somewhat light sensitive so reactions were conducted in the dark; the uranium(IV) compound [ n Pr 4 N] 4 [U(NCSe) 8 ] was also reported to be light sensitive [12]. Decomposition to red selenium powder was sometimes observed but the fate of the uranium was not determined.…”

“…Unfortunately, crystals grown from different solvents always proved to be twinned so refinement to a satisfactory standard was not possible, however it did prove atom connectivity ( Figure S1). During the course of one experiment, a few single crystals which had a different morphology were observed; these were separated by hand and the structure was solved to be [Et 4 …”

“…Moreover, the photophysical properties of uranyl were first used in ancient roman times in colored glass [1], whilst comprehensive understanding of the bonding, and therefore photophysical properties, has come from both experiment and theory. An authoritative review by Denning summarizes these fundamental developments [2], and further reviews cover recent results [3][4][5][6]. The photophysical properties of the uranyl ion have been elucidated from these studies and the optical properties are due to a ligand-to-metal charge transfer (LMCT) transition involving promotion of an electron from a bonding -yl oxygen orbital (σ u , σ g , π u and π g ) to a non-bonding 5f δ and 5f φ orbital on uranium.…”