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)(2)U[=N(4-(OPrC6H4)-Pr-i)](2), is readily accomplished with Al(C5Me5), forming the bridging uranium(IV)/aluminum(III) imido complex (C5Me5)(2)U[mu(2)-N(4-(OPrC6H4)-Pr-i)](2)Al(C5Me5). The structure and bonding of the bridging imido complex is examined with electrochemical measurements in tandem with density functional theory calculations.