Synthesis and Spectroscopic and Computational Characterization of the Chalcogenido-Substituted Analogues of the Uranyl Ion, [OUE]2+ (E = S, Se)
Synthesis and Spectroscopic and Computational Characterization of the Chalcogenido-Substituted Analogues of the Uranyl Ion, [OUE]2+ (E = S, Se)
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DOI：
10.1021/ja402068j
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发表时间：
2013-04-10
影响因子：
15
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
--
作者：
Brown, Jessie L.;Fortier, Skye;Hayton, Trevor W.
在THF中向[Cp-2*Co][U(O)(NR2)(3)] （R = SiMe3）中加入E (E = 0.125S(8), Se)，可分离出硫代铀酰类似物[Cp-2*Co][U(O)(E)(NR2)(3)] [E = S(1), Se(2)]，产率较高。同样，在[Cp-2*Co][U(O)(NR2)(3)]中加入1等量的2,2,6,6-四甲基哌啶-1-氧（TEMPO），得到铀酰配合物[Cp-2*Co][UO2(NR2)(3)](3)。所有的配合物都被充分表征，包括x射线晶体学分析。它们还通过密度泛函理论计算进行了分析，以探测16族下降时U-E键的变化。
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.