Trivalent Uranium Phenylchalcogenide Complexes: Exploring the Bonding and Reactivity with CS2 in the Tp*2UEPh Series (E = O, S, Se, Te)

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• 作者：Ellen M. Matson ; Andrew T. Breshears ; John J. Kiernicki ; Brian S. Newell ; Phillip E. Fanwick ; Matthew P. Shores ; Justin R. Walensky ; Suzanne C. Bart
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：December 15, 2014
• 年：2014
• 卷：53
• 期：24
• 页码：12977-12985
• 全文大小：472K
• ISSN：1520-510X

文摘

The trivalent uranium phenylchalcogenide series, Tp*₂UEPh (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, E = O (1), S (2), Se (3), Te (4)), has been synthesized to investigate the nature of the U鈥揈 bond. All compounds have been characterized by ¹H NMR, infrared and electronic absorption spectroscopies, and in the case of 4, X-ray crystallography. Compound 4 was also studied by SQUID magnetometry. Computational studies establish Mulliken spin densities for the uranium centers ranging from 3.005 to 3.027 (B3LYP), consistent for uranium鈥揷halcogenide bonds that are primarily ionic in nature, with a small covalent contribution. The reactivity of 2鈥?b>4 toward carbon disulfide was also investigated and showed reversible CS₂ insertion into the U(III)鈥揈 bond, forming Tp*₂U(魏²-S₂CEPh) (E = S (5), Se (6), Te (7)). Compound 5 was characterized crystallographically.