Oxo ligand functionalization in the uranyl ion (UO22+)

Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

“…13 While characterization of this reaction's product revealed an octahedral U(VI) atom ligated by three phenolate oxygens from each of two calixarene ligands, the mechanism of activation was not understood. 13,14 Drawing from this report and from previously performed gas-phase mono-activation reactions, we sought to investigate potential mechanisms associated with the cleavage of both UO 2 2+ oxo bonds, using chelated UO 2 2+ as a starting reagent. Here, we describe the non-reductive UO 2 2+ oxo activation by an octadentate catecholamide ligand, 3,4,3-LI(CAM), leading to the cleavage of both U=O bonds and the formation of a formal U 6+ chelate in the gas-phase.…”

Perturbation of the O–U–O Angle in Uranyl by Coordination to a 12-Membered Macrocycle

“…This technique has proven to be useful for probing the relative strengths of the U=O bond in the uranyl fragment. 48 Raman spectroscopic data for complexes 1 -4 are shown in Figure S11). Also observed in this spectrum is a singlet at 3.57 ppm, which is assignable to the two methyl substituents.…”

Synthesis and electronic structure determination of uranium(vi) ligand radical complexes

“…2 The chemistry of the UO 2 2+ ion, with an emphasis on structural modification of the uranyl oxo ligands (O=U=O), and ligand coordination in the equatorial plane, has been previously reviewed. 3 The stabilization and reactivity of uranium, in the U III , U IV , U V and U VI oxidation states, has attracted much research interest in recent years. 4 Interest in the coordination chemistry of uranium is also due to the need for its safe extraction from soil and water, and stabilization of nuclear waste.…”