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Guo, Fu‐Sheng; Tsoureas, Nikolaos; Huang, Guo‐Zhang; Tong, Ming‐Liang; Mansikkamäki, Akseli; Layfield, Richard A.
Angewandte Chemie, February 3, 2020, Letnik: 59, Številka: 6Journal Article
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 of 2 is 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 5f3 6d1. Appreciable covalent contributions to the metal‐ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbitals with essentially pure 5f character, the fourth electron resides in an orbital defined by strong 7s‐6dz2 mixing. A new generation: Reduction of the uranium(III) metallocene (η5‐C5iPr5)2UI with potassium graphite produces the “second‐generation” uranocene (η5‐C5iPr5)2U, which contains uranium in the formal divalent oxidation state. The geometry of (η5‐C5iPr5)2U is that of a perfectly linear bis(cyclopentadienyl) sandwich complex.
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