Hsueh Fang-Che, Barluzzi Luciano, Rajeshkumar Thayalan, Scopelliti Rosario, Zivkovic Ivica, Maron Laurent, Mazzanti Marinella
Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Laboratoire de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquées, 31077 Toulouse, Cedex 4, France.
Dalton Trans. 2024 Aug 13;53(32):13416-13426. doi: 10.1039/d4dt01819b.
Single-atom (group 15 and group 16 anions) bridged dimetallic complexes of low oxidation state uranium provide a convenient route to implement multielectron transfer and promote magnetic communication in uranium chemistry, but remain extremely rare. Here we report the synthesis, redox and magnetic properties of N, O, and S bridged diuranium complexes supported by bulky aryloxide ligands. The U(IV)/U(IV) nitride [Cs(THF)][(U(OAr))(μ-N)], 1 could be prepared and characterized but could not be reduced. Reduction of the neutral U(IV)/U(IV) complexes [(U(OAr))(μ-X)] A (X = O) and B (X = S) led to the isolation and characterization of the U(IV)/U(III) and U(III)/U(III) analogues. Complexes [(K(THF))(U(OAr))(μ-S)], 5 and [K(2.2.2-cryptand)][(U(OAr))(μ-S)], 6 are the first examples of U(III) sulphide bridged complexes. Computational studies and redox properties allow the reactivity of the dimetallic complexes to be related to their electronic structure.
低氧化态铀的单原子（第15族和第16族阴离子）桥联双金属配合物为在铀化学中实现多电子转移和促进磁通信提供了一条便捷途径，但仍然极为罕见。在此，我们报道了由庞大的芳氧基配体支撑的N、O和S桥联双铀配合物的合成、氧化还原和磁性性质。U(IV)/U(IV)氮化物[Cs(THF)][(U(OAr))(μ-N)]，1可以制备并表征，但无法被还原。中性U(IV)/U(IV)配合物[(U(OAr))(μ-X)] A（X = O）和B（X = S）的还原导致了U(IV)/U(III)和U(III)/U(III)类似物的分离和表征。配合物[(K(THF))(U(OAr))(μ-S)]，5和[K(2.2.2-穴醚)][(U(OAr))(μ-S)]，6是U(III)硫化物桥联配合物的首例。计算研究和氧化还原性质使得双金属配合物的反应性与其电子结构相关联。
