Synthesis, Molecular and Electronic Structure of UV(O)[N(SiMe3)2]3
Synthesis, Molecular and Electronic Structure of UV(O)[N(SiMe3)2]3
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DOI：
10.1021/ic201936j
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发表时间：
2012-02-06
影响因子：
4.6
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
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作者：
Fortier, Skye;Brown, Jessie L.;Hayton, Trevor W.
在己烷中的U(NR2)(3)中加入1等量的2,2,6,6-四甲基哌啶-1-氧（TEMPO），得到U(O)(NR2)(3)(2)，收率为73%。配合物2是末端U(V)氧配合物的罕见例子。相反，在戊烷中的U(NR2)(3) （R = SiMe3）中加入1等量的Me3NO，生成U（IV）桥接氧[(NR2)(3)U](2)(mu-O)(3)，产率中等。在该反应中还生成了低产率的U（IV）碘化物络合物U(I)(NR2)(3)(4)。4中的碘化物配体可能来自残留的NaI，存在于U(NR2)(3)起始材料中。在U(NR2)(3)的正己烷溶液中加入0.5等量的I-2可合理生成配合物4，并可以中等产率分离为棕褐色结晶固体。测量了2、3、4的固态分子结构和磁化率。此外，利用密度泛函理论（DFT）方法研究了2和3的电子结构。
Addition of 1 equiv of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to U(NR2)(3) in hexanes affords U(O)(NR2)(3) (2), which can be isolated in 73% yield. Complex 2 is a rare example of a terminal U(V) oxo complex. In contrast, addition of 1 equiv of Me3NO to U(NR2)(3) (R = SiMe3) in pentane generates the U(IV) bridging oxo [(NR2)(3)U](2)(mu-O) (3) in moderate yields. Also formed in this reaction, in low yield, is the U(IV) iodide complex U(I)(NR2)(3) (4). The iodide ligand in 4 likely originates from residual NaI, present in the U(NR2)(3) starting material. Complex 4 can be generated rationally by addition of 0.5 equiv of I-2 to a hexane solution of U(NR2)(3), where it can be isolated in moderate yield as a tan crystalline solid. The solid-state molecular structures and magnetic susceptibilities of 2, 3, and 4 have been measured. In addition, the electronic structures of 2 and 3 have been investigated by density functional theory (DFT) methods.