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The structure of the uranyl ion (UO 2  2+ ) has been the topic of investigation for almost a century. Since the first structural study of uranyl in 1935, over 4000 uranyl complexes have been characterized by X-ray crystallography. The vast majority of these complexes feature a linear uranyl group (e.g., O yl -U-O yl = 180°); however, there are a handful of complexes that feature much more acute O yl -U-O yl angles. In fact, the smallest experimentally observed O yl -U-O yl angles are ca. 161°. This Frontier Article catalogs every reported uranyl complex that features an O yl -U-O yl angle below 172°, and attempts to rationalize the origins of the observed O yl -U-O yl bending. In particular, I describe two distinct causes of O yl -U-O yl bending: (1) bending that occurs as a result of unfavourable steric interactions between the equatorial co-ligands and the uranyl oxo groups; and (2) bending that appears to have an electronic origin. In addition, I describe several possible avenues for future investigation. Understanding the effect that O yl -U-O yl bending has on uranyl electronic structure could ultimately provide insight into several unique aspects of the uranyl ion, such as the inverse trans influence and the involvement of the "pseudo-core" U6p orbitals in U-O yl bonding.

Understanding the origins of Oyl–U–Oylbending in the uranyl (UO22+) ion

Understanding the origins of O_yl–U–O_ylbending in the uranyl (UO₂²⁺) ion