Uranocenium: Synthesis, Structure, and Chemical Bonding

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...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-07, Vol.58 (30), p.10163-10167
Main Authors: Guo, Fu‐Sheng, Chen, Yan‐Cong, Tong, Ming‐Liang, Mansikkamäki, Akseli, Layfield, Richard A.
Format: Article
Language:English
Subjects:
Anisotropy
Bonding strength
chemical bonding
Chemical bonds
Chemical synthesis
electronic structure
Iodides
Ligands
Magnetic fields
Magnetic induction
Magnetic properties
Magnetic relaxation
Magnetism
metallocenes
Orbitals
Organic chemistry
Uranium
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Summary: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.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201903681