Uranocenium: Synthesis, Structure, and Chemical Bonding
Uranocenium: Synthesis, Structure, and Chemical Bonding
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铀铍：合成、结构和化学键合
DOI：
10.1002/ange.201903681
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发表时间：
2019
影响因子：
--
通讯作者：
Guo F
中科院分区：
文献类型：
--
作者：
Guo F
从[(η5‐C5iPr5)2UI](1)中提取碘化物，生成阳离子铀（III）茂金属[(η5‐C5iPr5)2U]+(2)，作为[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，在铀上的弯曲角为167.82°。对in2成键的分析表明，铀5f轨道强烈分裂并与配体轨道混合，从而导致共价对成键的贡献不可忽略。对2f的动态磁性能的研究表明，5f共价导致了各向异性的部分猝灭和零外加磁场下的快速磁弛豫。施加磁场导致拉曼过程的显性弛豫。
Abstraction 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 of2consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in2showed 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 of2revealed 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.