Guo Fu-Sheng, Chen Yan-Cong, Tong Ming-Liang, Mansikkamäki Akseli, Layfield Richard A
Department of Chemistry, University of Sussex, Falmer, Brighton, BN1 9QR, UK.
Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, P. R. China.
Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10163-10167. doi: 10.1002/anie.201903681. Epub 2019 Jun 24.
Abstraction of iodide from [(η -C Pr ) UI] (1) produced the cationic uranium(III) metallocene [(η -C Pr ) U] (2) as a salt of [B(C F ) ] . 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.
从[(η⁵-C₅Pr₅)UI]（1）中提取碘化物得到阳离子铀（III）茂金属[(η⁵-C₅Pr₅)U]（2），它是[B(C₆F₅)₄]⁻的盐。2的结构由不对称键合的环戊二烯基配体组成，铀处的弯曲角度为167.82°。对2中键合的分析表明，铀的5f轨道强烈分裂并与配体轨道混合，从而导致键合中不可忽略的共价贡献。对2的动态磁性质的研究表明，5f共价性导致零外磁场下部分淬灭的各向异性和快速磁弛豫。施加磁场会导致拉曼过程占主导的弛豫。
