Chalcogen Atom Transfer to Uranium(III): Synthesis and Characterization of [(R2N)3U]2(μ-E) and [(R2N)3U]2(μ-η2:η2-S2) (R = SiMe3; E = S, Se, Te)
Chalcogen Atom Transfer to Uranium(III): Synthesis and Characterization of [(R2N)3U]2(μ-E) and [(R2N)3U]2(μ-η2:η2-S2) (R = SiMe3; E = S, Se, Te)
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DOI：
10.1021/om301004q
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发表时间：
2013-03-11
期刊：
影响因子：
2.8
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
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作者：
Brown, Jessie L.;Wu, Guang;Hayton, Trevor W.
将0.0625当量的S-8添加到Et 2 O中的U（NR 2）（3）（R = SiMe 3）中产生[（R2 N）（3）U]（2）（mu-S）（1），其可以通过从冷Et 2 O中结晶以中等产率分离。有趣的是，如果U（NR 2）（3）起始材料被U（IV）金属配合物U（CH 2SiMe 2NSiMe 3）（NR 2）（2）污染，则在与S-8的反应中也形成第二产物，即[（R2 N）（3）U]（2）（μ-η（2）：η（2）-S-2）（2）。由于该物质不溶于Et 2 O，因此可以低收率从1中分离出来。最后，向U（NR 2）（3）（R = SiMe 3）中加入0.5当量的E（E = Se，Te）导致以中等产率形成[（R2 N）（3）U]（2）（μ-E）（E = Se（3），Te（4））。配合物1-4进行了充分的表征，包括通过X射线晶体学分析。
Addition of 0.0625 equiv of S-8 to U(NR2)(3) (R = SiMe3) in Et2O generates [(R2N)(3)U](2)(mu-S) (1), which can be isolated in moderate yield by crystallization from cold Et2O. Interestingly, if the U(NR2)(3) starting material is contaminated with the U(IV) metallacycle U(CH2SiMe2NSiMe3)(NR2)(2), then a second product is also formed in the reaction with S-8, namely, [(R2N)(3)U](2)(mu-eta(2):eta(2)-S-2) (2). This species can be separated from 1, in low yield, by virtue of its insolubility in Et2O. Finally, addition of 0.5 equiv of E (E = Se, Te) to U(NR2)(3) (R = SiMe3) results in the formation of [(R2N)(3)U](2)(mu-E) (E = Se (3), Te (4)) in moderate yields. Complexes 1-4 were fully characterized, including analysis by X-ray crystallography.