Destruction of the Uranyl Moiety in a U(V) "Cation-Cation" Interaction

A gas-phase uranyl peroxide dimer supported by three 12-crown-4 ether (12C4) ligands, [(UO₂)₂(O₂)(12C4)₃)]²⁺ (A), 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 A resulted in elimination of the bridging 12C4 to yield a uranyl peroxide dimer with two terminal donor ligands, [(12C4)(UO₂)(O₂)(UO₂)(12C4)]²⁺ (B). Remarkably, CID of B resulted in elimination of the bridging peroxide concomitant with reduction of U(VI) to U(V) in C, [(12C4)(UO₂)(UO₂)(12C4)]²⁺. DFT studies indicate that in C there is direct interaction between the two UO₂⁺ 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 PaO₂⁺ but is less feasible for transuranic actinyls.