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La Pierre, Henry S.; Scheurer, Andreas; Heinemann, Frank W.; Hieringer, Wolfgang; Meyer, Karsten
Angewandte Chemie (International ed.), July 7, 2014, Letnik: 53, Številka: 28Journal Article
The low‐temperature (<−35 °C) reduction of the trivalent uranium monoarene complex {(Ad,MeArO)3mes}U (1), with potassium spheres in the presence of a slight excess of 2.2.2‐cryptand, affords the quantitative conversion of 1 into the uranium(II) monoarene complex K(2.2.2‐crypt)((Ad,MeArO)3mes)U (1‐K). The molecular and electronic structure of 1‐K was established experimentally by single‐crystal X‐ray diffraction, variable‐temperature 1H NMR and X‐band EPR spectroscopy, solution‐state and solid‐state magnetism studies, and optical absorption spectroscopy. The electronic structure of the complex was further investigated by DFT calculations. The complete body of evidence confirms that 1‐K is a uranium(II) monoarene complex with a 5f 4 electronic configuration supported by δ backbonding and that the nearly reversible, room‐temperature reduction observed for 1 at −2.495 V vs. Fc/Fc+ is principally metal‐centered. U2 rocks: The molecular and electronic structure of a uranium(II) monoarene complex with a 5f 4 electronic configuration supported by δ backbonding was established experimentally by single‐crystal X‐ray diffraction, variable‐temperature 1H NMR and X‐band EPR spectroscopy, solution‐state and solid‐state magnetism studies, and optical absorption spectroscopy. The electronic structure of the complex was further investigated by DFT calculations.
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