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Uranocenium: Synthesis, Structure, and Chemical Bonding
Author(s) -
Guo FuSheng,
Chen YanCong,
Tong MingLiang,
Mansikkamäki Akseli,
Layfield Richard A.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201903681
Subject(s) - chemistry , cyclopentadienyl complex , covalent bond , crystallography , atomic orbital , metallocene , raman spectroscopy , relaxation (psychology) , uranium , computational chemistry , materials science , electron , physics , polymerization , metallurgy , organic chemistry , psychology , social psychology , polymer , quantum mechanics , optics , catalysis
Abstraction of iodide from [(η 5 ‐C 5 i Pr 5 ) 2 UI] ( 1 ) produced the cationic uranium(III) metallocene [(η 5 ‐C 5 i Pr 5 ) 2 U] + ( 2 ) as a salt of [B(C 6 F 5 ) 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.