Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric DifferentiationThe following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization: [UO 2(12C4) 2] 2+and [UO 2(12C4) 2(OH)] +. Collision-induced dissociation (CID) of the dication resulted in [UO 2(12C4-H)] +(12C4-H is a 12C4 that has lost one H), which spontaneously adds water to yield [UO 2(12C4-H)(H 2O)] +. The latter has the same composition as complex [UO 2(12C4)(OH)] + produced by CID of [UO 2(12C4) 2(OH)] + but exhibits different reactivity with water. The postulated structures as isomeric [UO 2(12C4-H)(H 2O)] + and [UO 2(12C4)(OH)] + were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. Themore »
Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U 6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theorymore »
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