Synthesis of organo-uranium(II) species in the gas-phase using reactions between [UH] and nitriles.

One challenge in the quest to map the intrinsic reactivity of model actinide species has been the controlled synthesis of organo-actinide ions in the gas phase. We report here evidence that a series of gas-phase, σ-bonded [U-R] species (where R = CH, CH, CH, CH, or CH) can be generated for subsequent study of ion-molecule chemistry by using preparative tandem mass spectrometry (PTMS) ion-molecule reactions between [UH] and a series of nitriles. Density functional theory calculations support the hypothesis that the [U-R] ions are created in a pathway that involves intramolecular hydride attack and the elimination of neutral HCN.

Conversion of a UO Precursor to UH and U Using Tandem Mass Spectrometry to Remove Both "yl" Oxo Ligands.

Multiple-stage collision-induced dissociation (CID) of a uranyl propiolate cation, [UO(OC-C≡CH)], can be used to prepare the U-methylidyne species [O═U≡CH] [ , , 796-805]. Here, we report that CID of [O═U≡CH] causes elimination of CO to create [UH], followed by a loss of H to generate U. A feasible, multiple-step pathway for the generation of [UH] was identified using DFT calculations.