Synthesis, Structure, and Magnetism of an f Element Nitrosyl Complex, (C5Me4H)3UNO

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• 作者：Nathan A. Siladke ; Katie R. Meihaus ; Joseph W. Ziller ; Ming Fang ; Filipp Furche ; Jeffrey R. Long ; William J. Evans
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：January 18, 2012
• 年：2012
• 卷：134
• 期：2
• 页码：1243-1249
• 全文大小：395K
• 年卷期：v.134,no.2(January 18, 2012)
• ISSN：1520-5126

文摘

(C₅Me₄H)₃U, 1, reacts with 1 equiv of NO to form the first f element nitrosyl complex (C₅Me₄H)₃UNO, 2. X-ray crystallography revealed a 180掳 U鈥揘鈥揙 bond angle, typical for (NO)¹⁺ complexes. However, 2 has a 1.231(5) 脜 N鈺怬 distance in the range for (NO)^{1鈥?/sup> complexes and a short 2.013(4) 脜 U鈥揘 bond like the U鈺怤 bond of uranium imido complexes. Structural, spectroscopic, and magnetic data as well as DFT calculations suggest that reduction of NO by U3+ has occurred to form a U4+ complex of (NO)1鈥?/sup> that has 蟺 interactions between uranium 5f orbitals and NO 蟺* orbitals. These bonding interactions account for the linear geometry and short U鈥揘 bond. The complex displays temperature-independent paramagnetism with a magnetic moment of 1.36 渭_B at room temperature. Complex 2 reacts with Al₂Me₆ to form the adduct (C₅Me₄H)₃UNO(AlMe₃), 3.}