Bubas Amanda R, Perez Evan, Metzler Luke J, Rissler Scott D, Van Stipdonk Michael J
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania, USA.
Department of Chemistry, University of Utah, Salt Lake City, Utah, USA.
J Mass Spectrom. 2021 Mar;56(3):e4705. doi: 10.1002/jms.4705.
Electrospray ionization (ESI) can produce a wide range of gas-phase uranyl (UO ) complexes for tandem mass spectrometry studies of intrinsic structure and reactivity. We describe here the formation and collision-induced dissociation (CID) of [UO (NO ) ] and [UO (NO ) (O )] . Multiple-stage CID experiments reveal that the complexes dissociate in reactions that involve elimination of O , NO , or NO , and subsequent reactions of interesting uranyl-oxo product ions with (neutral) H O and/or O were investigated. Density functional theory (DFT) calculations reproduce experimental results and show that dissociation of nitrate ligands, with ejection of neutral NO , is favored for both [UO (NO ) ] and [UO (NO ) (O )] . DFT calculations also suggest that H O adducts to products such as [UO (O)(NO )] spontaneously rearrange to create dihydroxides and that addition of O is favored over addition of H O to formally U(V) species.
电喷雾电离（ESI）可产生多种气相铀酰（UO ）配合物，用于对其内在结构和反应活性进行串联质谱研究。我们在此描述了[UO (NO ) ]和[UO (NO ) (O )] 的形成及碰撞诱导解离（CID）过程。多级CID实验表明，这些配合物在涉及消除O 、NO 或NO 的反应中发生解离，并对有趣的铀酰-氧产物离子与（中性）H O和/或O 的后续反应进行了研究。密度泛函理论（DFT）计算重现了实验结果，并表明对于[UO (NO ) ]和[UO (NO ) (O )] ，伴随着中性NO 的射出，硝酸盐配体的解离是有利的。DFT计算还表明，诸如[UO (O)(NO )] 等产物的H O加合物会自发重排形成二氢氧化物，并且对于形式上的U(V)物种，O 的添加比H O的添加更有利。
