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|Title:||Single-Electron Uranyl Reduction by a Rare-Earth Cation|
|Authors:||ARNOLD Polly L.; HOLLIS Emmalina; WHITE Fraser, J.; MAGNANI Nicola; CACIUFFO Roberto; LOVE Jason B.|
|Citation:||Angewandte Chemie vol. 123 no. 4 p. 917-920|
|Publisher:||WILEY-VCH Verlag GmbH & Co. KGaA|
|Type:||Articles in periodicals and books|
|Abstract:||Unlike their transition-metal analogues, the oxo groups of the uranyl dication, [UO2]2+, which has a linear geometry and short, strong U-O bonds are commonly considered inert. Very little Lewis base character has been demonstrated for the uranyl oxo groups,[2,3] which makes them poor models for the heavier, highly radioactive transuranic actinyl cations such as neptunyl [NpO2]n+ (n=1, 2).[4, 5] The heavier actinyls are important components in nuclear waste and demonstrate oxo basicity that can give rise to poorly understood cluster formation and problems in nuclear waste PUREX separation processes. However, it has been shown recently that the more Lewis basic, pentavalent uranyl cation, [UO2]+, can be stabilized indefinitely using suitable equatorial-binding ligands and anaerobic conditions.[7,8] Usually the [UO2]+ cation decomposes by disproportionation, which is also a poorly understood process, but is important in the precipitation of uranium salts out of aqueous environments.[9, 10] The disproportionation is suggested, by analogy with the transuranic metal oxo Lewis base behavior, to involve the formation of cation–cation interactions (CCIs)[11, 12] in which the oxo groups ligate to adjacent actinyl centers forming diamond (A) or T-shaped (B) dimers or clusters which can then allow the transfer of protons and electrons between metals, such as in C.|
|JRC Institute:||Nuclear Safety and Security|
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