Electrospray ionization (ESI) can produce a wide range of gas‐phase uranyl (UO₂²⁺) complexes for tandem mass spectrometry studies of intrinsic structure and reactivity. We describe here the formation and collision‐induced dissociation (CID) of [UO₂(NO₃)₃]⁻ and [UO₂(NO₃)₂(O₂)]⁻. Multiple‐stage CID experiments reveal that the complexes dissociate in reactions that involve elimination of O₂, NO₂, or NO₃, and subsequent reactions of interesting uranyl‐oxo product ions with (neutral) H₂O and/or O₂ were investigated. Density functional theory (DFT) calculations reproduce experimental results and show that dissociation of nitrate ligands, with ejection of neutral NO₂, is favored for both [UO₂(NO₃)₃]⁻ and [UO₂(NO₃)₂(O₂)]⁻. DFT calculations also suggest that H₂O adducts to products such as [UO₂(O)(NO₃)]⁻ spontaneously rearrange to create dihydroxides and that addition of O₂ is favored over addition of H₂O to formally U(V) species.

中文翻译：

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碰撞诱导的[UO2（NO3）3]-和[UO2（NO3）2（O2）]-的解离以及产物离子与H2O和O2的反应

电喷雾电离（ESI）可以产生多种气相铀酰（UO ₂ ²⁺）配合物，用于串联质谱研究固有结构和反应性。我们在这里描述[UO ₂（NO ₃）₃ ] ^-和[UO ₂（NO ₃）₂（O ₂）] ^-的形成和碰撞诱导解离（CID）。多阶段CID实验表明，络合物在涉及消除O ₂，NO ₂或NO _3的反应中解离，以及随后有趣的铀酰-氧代产物离子与（中性）H反应_研究了2 O和/或O ₂。密度泛函理论（DFT）计算重现了实验结果，结果表明，[UO ₂（NO ₃）₃ ] ^-和[UO ₂（NO ₃）₂（O ）都有利于硝酸盐配体的分解和中性NO _2的喷射。₂）] ^-。DFT计算还表明，H ₂ O加成产物会自动重排生成[UO ₂（O）（NO ₃）] ^-二氧化氢，并添加O ₂与在正式的U（V）物种中添加H ₂ O相比，它更受欢迎。