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 = CH₃, C₂H₃, C₂H₅, C₃H₇, or C₅H₆) can be generated for subsequent study of ion-molecule chemistry by using preparative tandem mass spectrometry (PTMSⁿ) 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 [UCH₃]⁺ readily undergoes hydrolysis, yielding cationic uranium hydroxide ([UOH]⁺) and methane (CH₄). Other possible reaction pathways, such as the spontaneous rearrangement to [HUCH₂]⁺, are shown by theoretical calculations to have energy barriers, strengthening the evidence for the formation of a σ-bonded [U–CH₃]⁺ complex in the gas-phase.

中文翻译：

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利用 [UH]+ 和腈之间的反应在气相中合成有机铀 （II） 物质


在寻求绘制模型锕系元素物种的内禀反应性的过程中，一个挑战是在气相中控制合成有机锕系元素离子。我们在这里报告的证据表明，通过使用制备串联质谱 （PTMSⁿ），可以产生一系列气相、σ键 [U–R]⁺ 物质（其中 R = CH₃、C₂H₃、C₂H₅、C₃H₇ 或 C₅H₆），用于离子分子化学的后续研究[UH]⁺ 与一系列腈之间的离子-分子反应。密度泛函理论计算支持以下假设：[U–R]⁺ 离子是在涉及分子内氢化物攻击和中性 HCN 消除的途径中产生的。随后的反应性实验表明，[UCH₃]⁺ 容易发生水解，产生阳离子氢氧化铀 （[UOH]⁺） 和甲烷 （CH₄）。理论计算表明，其他可能的反应途径，例如自发重排为 [胡 CH₂]⁺，具有能垒，这加强了在气相中形成σ键 [U–CH₃]⁺ 络合物的证据。