Two-Electron Reduction of a U(VI) Complex with Al(C5Me5)

The reduction of U­(VI) to U­(IV) is rare, especially in one step, and not observed electrochemically as a one-wave, two-electron couple. Here, we demonstrate that reduction of the uranium­(VI) bis­(imido) complex, (C5Me5)2U­[N­(4-OiPrC6H4)]2, is readily accomplished with Al­(C5Me5), forming the bridging uranium­(IV)/aluminum­(III) imido complex (C5Me5)2U­[μ2-N­(4-OiPrC6H4)]2Al­(C5Me5). The structure and bonding of the bridging imido complex is examined with electrochemical measurements in tandem with density functional theory calculations.将六价铀（U(VI)）还原为四价铀（U(IV)）的反应较为罕见，一步还原的过程尤为如此，且尚未被观测到以单波双电子氧化还原对的电化学形式存在。本研究证实，铀(VI)双亚氨基配合物(C₅Me₅)₂U[=N(4-OiPrC₆H₄)]₂可通过五甲基环戊二烯基铝（Al(C₅Me₅)）顺利实现还原，生成桥联型四价铀(IV)/三价铝(III)亚氨基配合物(C₅Me₅)₂U[μ₂-N(4-OiPrC₆H₄)]₂Al(C₅Me₅)。本研究通过电化学测试结合密度泛函理论（Density Functional Theory, DFT）计算，对该桥联亚氨基配合物的结构与成键特性进行了系统分析。