Accessing five oxidation states of uranium in a retained ligand framework

作者：Deng, Chong; Liang, Jiefeng; Sun, Rong; Wang, Yi; Fu, Peng-Xiang; Wang, Bing-Wu; Gao, Song; Huang, Wenliang^*

来源：Nature Communications, 2023, 14(1): 4657.

DOI：10.1038/s41467-023-40403-w

• VALENT ORGANOURANIUM COMPLEXES
• ELECTRONIC-STRUCTURE
• OXO COMPLEXES
• ARENE
• MOLECULE
• COORDINATION
• REACTIVITY
• REDUCTION
• CHEMISTRY
• REDOX

Understanding and exploiting the redox properties of uranium is of great importance but stabilizing both low and high valent uranium ions in a preserved ligand environment remains challenging. Here, the authors report the synthesis and characterisation of a series of uranium(II-VI) complexes supported by a tripodal tris(amido)arene ligand. @@@ 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 & delta; acceptor or a & pi; 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.

• 单位
  北京大学