Creation of Gas-Phase Organo-Uranium Species by Removal of "yl" Oxo Ligands From UO Carboxylate Precursor Ions.

Rationale: These experiments were conducted to measure the diversity of organo-U (IV) and U (III) ions created using multiple-stage tandem MS and collision-induced dissociation of halogen-substituted UO-phenide complexes [UO(CHFX)], X = Cl, Br, or I.

Methods: Samples of UO(OC-CHFX) were prepared by digesting UO with appropriate halogen-substituted carboxylic acids in deionized water. Solutions for ESI were created by diluting the digested sample in 50:50 HO/CHOH.

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.