Synthesis and Spectroscopic and Computational Characterization of the Chalcogenido-Substituted Analogues of the Uranyl Ion, [OUE]2+ (E = S, Se)

被引：75

作者：

Brown, Jessie L. ^{[1
]}

Fortier, Skye ^{[1
]}

Wu, Guang ^{[1
]}

Kaltsoyannis, Nikolas ^{[2
]}

Hayton, Trevor W. ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

[2] UCL, Christopher Ingold Labs, Dept Chem, London WC1H 0AJ, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 14期

基金：

美国国家科学基金会;

关键词：

DENSITY-FUNCTIONAL THEORY; ELECTRONIC-STRUCTURE; INFRARED-SPECTRA; IMIDO ANALOGS; COMPLEXES; LIGAND; SERIES; TE; DEOXYGENATION; ACTIVATION;

D O I：

10.1021/ja402068j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Addition of E (E = 0.125S(8), Se) to [Cp-2*Co][U(O)(NR2)(3)] (R = SiMe3) in THF results in the isolation of the chalcogen-substituted uranyl analogues [Cp-2*Co][U(O)(E)(NR2)(3)] [E = S (1), Se (2)] in good yields. Similarly, addition of 1 equiv of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to [Cp-2*Co][U(O)(NR2)(3)] affords the uranyl complex [Cp-2*Co][UO2(NR2)(3)] (3). All of the complexes were fully characterized, including analysis by X-ray crystallography. They were also analyzed by density functional theory calculations to probe the changes in the U-E bond as group 16 is descended.

引用

页码：5352 / 5355

页数：4

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