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Guo, Fu‐Sheng; Chen, Yan‐Cong; Tong, Ming‐Liang; Mansikkamäki, Akseli; Layfield, Richard A.
Angewandte Chemie International Edition, July 22, 2019, Letnik: 58, Številka: 30Journal Article
ion of iodide from (η5‐C5iPr5)2UI (1) produced the cationic uranium(III) metallocene (η5‐C5iPr5)2U+ (2) as a salt of B(C6F5)4−. The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non‐negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to dominant relaxation by a Raman process. Uranium sandwiches: ion of iodide from (η5‐C5iPr5)2UI produced the cationic uranium(III) metallocene (η5‐C5iPr5)2U+ as its B(C6F5)4− salt (see scheme). Appreciable covalency involving 5f and 6d orbitals in the uranocenium cation partially quenched the orbital angular momentum and led to slow magnetic relaxation in an applied field by a Raman mechanism.
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