Isolation of a Perfectly Linear Uranium(II) Metallocene
Isolation of a Perfectly Linear Uranium(II) Metallocene
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完美线性铀(II)茂金属的分离
DOI：
10.1002/ange.201912663
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发表时间：
2020
影响因子：
--
通讯作者：
Guo F
中科院分区：
文献类型：
--
作者：
Guo F
用钾石墨还原铀（III）茂金属[（η5-C5 iPr 5）2UI]（1）产生“第二代”二茂铀[（η5-C5 iPr 5）2U]（2），其含有形式二价氧化态的铀。2的几何结构是一个完美的线性双夹心配合物，电子光谱和密度泛函理论揭示了铀（II）的基态价电子构型为5 f36 d1。对金属-配体键的共价贡献是通过计算研究确定的，包括铀5 f和6d轨道的参与。虽然2中的三个未配对电子占据基本上纯5 f特征的轨道，但第四个电子位于由强7s-6d混合定义的轨道中。
Reduction of the uranium(III) metallocene [(η5‐C5iPr5)2UI] (1) with potassium graphite produces the “second‐generation” uranocene [(η5‐C5iPr5)2U] (2), which contains uranium in the formal divalent oxidation state. The geometry of2is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground‐state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f36d1. Appreciable covalent contributions to the metal‐ligand bonds were determined from a computational study of2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in2occupy orbitals with essentially pure 5f character, the fourth electron resides in an orbital defined by strong 7s‐6d mixing.