Control of Oxo-Group Functionalization and Reduction of the Uranyl Ion
Control of Oxo-Group Functionalization and Reduction of the Uranyl Ion
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DOI：
10.1021/acs.inorgchem.5b00420
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发表时间：
2015-04-06
影响因子：
4.6
通讯作者：
Love, Jason B.
中科院分区：
文献类型：
--
作者：
Arnold, Polly L.;Pecharman, Anne-Frederique;Love, Jason B.
铀酰络合物的大；室型n -8大环采用刚性的“吃豆人”几何结构，稳定了U-v氧化态，促进了单个铀酰氧基的化学反应。我们在此提出了单还原和氧硅化铀酰Pacman配合物的新的和直接的方法，并提出了解释产物形成的机制，以及使用替代试剂形成的副产物分布。其中一个氧基被单个金属阳离子功能化的铀酰（VI） Pacman配合物被激活为单电子还原。因此，添加第二等价物的刘易斯酸性金属配合物，如MgN ' (2) (N ' = N(SiMe3))，形成一个铀酰(V)配合物，其中两个氧基由于Mg - N键均解而被Mg官能化。相反，较少Lewis酸性配合物[Zn(N")Cl]的反应有利于形成较弱的U-O-Zn负相互作用，导致羟基的还原性硅化而不是碘化。光谱、晶体学和计算分析这些反应和氧化-金属化产物的其他途径分离，使我们能够提出机制，说明金属化或硅基的外氧基的途径。
Uranyl complexes of a large; compartmental N-8-macrocycle adopt a rigid, "Pacman" geometry that stabilizes the U-v oxidation state and promotes chemistty at a single uranyl oxo-group. We present here new and straightforward foutes to singly reduced and oxo-silyiated uranyl Pacman Complexes and propose mechanisms that account for the product formation, and the byproduct distributions that are formed using alternative reagents. Uranyl(VI) Pacman complexes in which one oxo-group is functionalized by a single metal cation are actiVated toward single-electron reduction. As such, the addition of a second equivalent of a Lewis acidic metal complex such as MgN"(2) (N" = N(SiMe3)) corms a uranyl(V) complex in Which both oxo-groups are Mg functionalized as a result of Mg N bond homolysis. In contrast, reactions with the less Lewis acidic complex [Zn(N")Cl] favor the formation of weaker U-O-Zn dative interactions, leading:to reductive silyiation of the tranyi oxo-group in preference to inetalation. Spectroscopic, crystallographic, and computational analysis of these reactions and of oxo-metalated products isolated by other routes have allowed us to propose mechanisms that account for pathways to metalation or Silylation of the exo-oxo group.