Uranocenium: Synthesis, Structure, and Chemical Bonding
Uranocenium: Synthesis, Structure, and Chemical Bonding
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DOI：
10.1002/anie.201903681
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发表时间：
2019-07-22
影响因子：
16.6
通讯作者：
Layfield, Richard A.
中科院分区：
文献类型：
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作者：
Guo, Fu-Sheng;Chen, Yan-Cong;Layfield, Richard A.
[（eta（5）-（C5 Pr 5）-Pr 1）（2）U]（1）的碘离子生成阳离子铀（III）茂金属[（eta（5）-（C5 Pr 5）-Pr 1）（2）U]（+）（2），其为[B（C6 F5）（4）]（-）的盐。2的结构由不对称键合的双金属配体和在铀上的167.82度的弯曲角组成。对2中键合的分析表明，铀5 f轨道强烈分裂并与配体轨道混合，从而导致对键合的不可忽略的共价贡献。动态磁性质的研究表明，在零外加磁场下，5 f共价导致部分淬灭的各向异性和快速磁弛豫。磁场的施加导致通过拉曼过程的主要弛豫。
ion of iodide from [(eta(5)-(C5Pr5)-Pr-i)(2)UI] (1) produced the cationic uranium(III) metallocene [(eta(5)-(C5Pr5)-Pr-i)(2)U](+) (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 degrees 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.