| Autor: |
Terhorst JG; Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA. vanstipdonkm@duq.edu., Corcovilos TA; Department of Physics, Duquesne University, Pittsburgh, PA 15282, USA., Lenze SJ; Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA. vanstipdonkm@duq.edu., van Stipdonk MJ; Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA. vanstipdonkm@duq.edu. |
| Abstrakt: |
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 3 , C 2 H 3 , C 2 H 5 , C 3 H 7 , or C 5 H 6 ) can be generated for subsequent study of ion-molecule chemistry by using preparative tandem mass spectrometry (PTMS n ) via 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. Subsequent reactivity experiments revealed that the [UCH 3 ] + readily undergoes hydrolysis, yielding cationic uranium hydroxide ([UOH] + ) and methane (CH 4 ). Other possible reaction pathways, such as the spontaneous rearrangement to [HUCH 2 ] + , are shown by theoretical calculations to have energy barriers, strengthening the evidence for the formation of a σ-bonded [U-CH 3 ] + complex in the gas-phase. |
