Hu Shu-Xian, Jian Jiwen, Li Jun, Gibson John K
Beijing Computational Science Research Center , Beijing 100193 , China.
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education , Tsinghua University , Beijing 100084 , China.
Inorg Chem. 2019 Aug 5;58(15):10148-10159. doi: 10.1021/acs.inorgchem.9b01265. Epub 2019 Jul 18.
A gas-phase uranyl peroxide dimer supported by three 12-crown-4 ether (12C4) ligands, [(UO)(O)(12C4))] (), was prepared by electrospray ionization. Density functional theory (DFT) indicates a structure with two terminal 12C4 and the third 12C4 bridging the uranium centers. Collision induced dissociation (CID) of resulted in elimination of the bridging 12C4 to yield a uranyl peroxide dimer with two terminal donor ligands, [(12C4)(UO)(O)(UO)(12C4)] (). Remarkably, CID of resulted in elimination of the bridging peroxide concomitant with reduction of U(VI) to U(V) in , [(12C4)(UO)(UO)(12C4)]. DFT studies indicate that in there is direct interaction between the two UO species, which can thus be considered as a so-called cation-cation interaction (CCI). This formal CCI, induced by tetradentate 12C4 ligands, corresponds to destruction of the linear uranyl moieties and creation of bridging U-O-U oxo-bonds. On the basis of the structural rearrangement to achieve the structurally extreme CCI interaction, it is predicted also to be accessible for PaO but is less feasible for transuranic actinyls.
通过电喷雾电离制备了一种由三个12-冠-4醚（12C4）配体支撑的气相过氧化铀酰二聚体，即[(UO)(O)(12C4))]（）。密度泛函理论（DFT）表明其结构为两个末端12C4以及第三个12C4桥连铀中心。对（）进行碰撞诱导解离（CID），导致桥连的12C4消除，生成具有两个末端供体配体的过氧化铀酰二聚体，即[(12C4)(UO)(O)(UO)(12C4)]（）。值得注意的是，对（）进行CID时，桥连过氧化物消除，同时（）中的U(VI)还原为U(V)，生成[(12C4)(UO)(UO)(12C4)]。DFT研究表明，在（）中两个UO物种之间存在直接相互作用，因此可被视为一种所谓的阳离子-阳离子相互作用（CCI）。这种由四齿12C4配体诱导的形式上的CCI，对应于线性铀酰部分的破坏以及桥连U-O-U氧键的形成。基于实现结构上极端CCI相互作用的结构重排，预计PaO也可实现，但对于超铀酰基则不太可行。
