Accessing five oxidation states of uranium in a retained ligand framework

• Published in: Nature communications Vol. 14; no. 1; p. 4657
• Main Authors: Deng, Chong, Liang, Jiefeng, Sun, Rong, Wang, Yi, Fu, Peng-Xiang, Wang, Bing-Wu, Gao, Song, Huang, Wenliang
• Format: Journal Article
• Language: English
• Published: England Nature Publishing Group 03.08.2023; Nature Publishing Group UK; Nature Portfolio
• Subjects: Catalysis; Ions; Ligands; Oxidation; Redox properties; Synthesis; Uranium
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-40403-w

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.