铀
化学
结晶学
电子顺磁共振
电子结构
钍
吸收光谱法
金属
物理化学
磁性
光谱学
钾
材料科学
核磁共振
计算化学
物理
有机化学
量子力学
冶金
作者
Henry S. La Pierre,Andreas Scheurer,Frank W. Heinemann,Wolfgang Hieringer,Karsten Meyer
标识
DOI:10.1002/anie.201402050
摘要
The low-temperature (<-35 °C) reduction of the trivalent uranium monoarene complex [{((Ad,Me) ArO)3 mes}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,Me) ArO)3 mes)U] (1-K). The molecular and electronic structure of 1-K was established experimentally by single-crystal X-ray diffraction, variable-temperature (1) H 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.
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