Subtle Interactions and Electron Transfer between U III , Np III , or Pu III and Uranyl Mediated by the Oxo Group
Subtle Interactions and Electron Transfer between U III , Np III , or Pu III and Uranyl Mediated by the Oxo Group
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U III 、Np III 或 Pu III 与铀酰基之间由氧代基团介导的微妙相互作用和电子转移
DOI：
10.1002/ange.201607022
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发表时间：
2016
影响因子：
--
通讯作者：
Arnold P
中科院分区：
文献类型：
--
作者：
Arnold P
发现并解释了AnCp 3（An=U，Np，Pu; Cp= C5 H5）中还原AnIII中心与配合物[（UO 2）（THF）（H2 L）]（L=“Pacman”Schiff碱聚吡咯大环）中铀酰（VI）二价阳离子氧结合和还原能力的显著差异。这是第一次用另一种锕系阳离子对铀酰氧进行选择性官能化。首先从理论和实验相结合的角度解释了相互矛盾的电子结构数据。从Cp 3U的完全单电子转移形成UIV-铀酰（V）化合物，其在低于4 K时表现为UV局部单分子磁体。 Cp 3 Np基团在氧代配位时的还原程度要小得多，并指定了NpIII‐铀（VI）配价键。溶液NMR和NIR光谱表明NpIVUV，但单晶X射线衍射和SQUID磁力测定表明NpIII-UV归属。DFT计算的Hirshfeld电荷和自旋密度分析表明半个电子已经转移，这些解释了氢核自旋密度贡献的强烈移动NMR光谱。PuIII-UV相互作用太弱，在THF溶剂中无法观察到，与计算的预测一致。
A dramatic difference in the ability of the reducing AnIIIcenter in AnCp3(An=U, Np, Pu; Cp=C5H5) to oxo‐bind and reduce the uranyl(VI) dication in the complex [(UO2)(THF)(H2L)] (L=“Pacman” Schiff‐base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At‐first contradictory electronic structural data are explained by combining theory and experiment. Complete one‐electron transfer from Cp3U forms the UIV‐uranyl(V) compound that behaves as a UV‐localized single molecule magnet below 4 K. The extent of reduction by the Cp3Np group upon oxo‐coordination is much less, with a NpIII‐uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest NpIVUVbut single‐crystal X‐ray diffraction and SQUID magnetometry suggest a NpIII‐UVIassignment. DFT‐calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The PuIII–UVIinteraction is too weak to be observed in THF solvent, in agreement with calculated predictions.