Accessing five oxidation states of uranium in a retained ligand framework

Abstract Understanding and exploiting the redox properties of uranium is of great importance because uranium has a wide range of possible oxidation states and holds great potential for small molecule activation and catalysis. However, it remains challenging to stabilise both low and high-valent uranium ions in a preserved ligand environment. Herein we report the synthesis and characterisation of a series of uranium(II–VI) complexes supported by a tripodal tris(amido)arene ligand. In addition, one- or two-electron redox transformations could be achieved with these compounds. Moreover, combined experimental and theoretical studies unveiled that the ambiphilic uranium–arene interactions are the key to balance the stabilisation of low and high-valent uranium, with the anchoring arene acting as a δ acceptor or a π donor. Our results reinforce the design strategy to incorporate metal–arene interactions in stabilising multiple oxidation states, and open up new avenues to explore the redox chemistry of uranium.