Subtle Interactions and Electron Transfer between U^III, Np^III, or Pu^III and Uranyl Mediated by the Oxo Group

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• 作者：Prof. Polly L. Arnold ; Michał S. Dutkiewicz ; Dr. Markus Zegke ; Dr. Olaf Walter ; Dr. Christos Apostolidis ; Dr. Emmalina Hollis ; Dr. Anne-Fré ; derique Pé ; charman ; Dr. Nicola Magnani ; Dr. Jean-Christophe Griveau ; Dr. Eric Colineau ; Prof. Roberto Caciuffo ; Xiaobin Zhang ; Prof. Georg Schreckenbach and Prof. Jason B. Love
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：October 4, 2016
• 年：2016
• 卷：55
• 期：41
• 页码：12797-12801
• 全文大小：1492K
• ISSN：1521-3773

文摘

A dramatic difference in the ability of the reducing An^III center 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 U^IV-uranyl(V) compound that behaves as a U^V-localized single molecule magnet below 4 K. The extent of reduction by the Cp₃Np group upon oxo-coordination is much less, with a Np^III-uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np^IVU^V but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np^III-U^VI assignment. 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 Pu^III–U^VI interaction is too weak to be observed in THF solvent, in agreement with calculated predictions.