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Collision‐induced dissociation of [UO 2 (NO 3 ) 3 ] − and [UO 2 (NO 3 ) 2 (O 2 )] − and reactions of product ions with H 2 O and O 2
Author(s) -
Bubas Amanda R.,
Perez Evan,
Metzler Luke J.,
Rissler Scott D.,
Van Stipdonk Michael J.
Publication year - 2021
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.4705
Subject(s) - chemistry , uranyl , dissociation (chemistry) , collision induced dissociation , ion , mass spectrometry , adduct , tandem mass spectrometry , electrospray ionization , uranyl nitrate , density functional theory , analytical chemistry (journal) , crystallography , inorganic chemistry , computational chemistry , uranium , organic chemistry , chromatography , materials science , metallurgy
Electrospray ionization (ESI) can produce a wide range of gas‐phase uranyl (UO 2 2+ ) complexes for tandem mass spectrometry studies of intrinsic structure and reactivity. We describe here the formation and collision‐induced dissociation (CID) of [UO 2 (NO 3 ) 3 ] − and [UO 2 (NO 3 ) 2 (O 2 )] − . Multiple‐stage CID experiments reveal that the complexes dissociate in reactions that involve elimination of O 2 , NO 2 , or NO 3 , and subsequent reactions of interesting uranyl‐oxo product ions with (neutral) H 2 O and/or O 2 were investigated. Density functional theory (DFT) calculations reproduce experimental results and show that dissociation of nitrate ligands, with ejection of neutral NO 2 , is favored for both [UO 2 (NO 3 ) 3 ] − and [UO 2 (NO 3 ) 2 (O 2 )] − . DFT calculations also suggest that H 2 O adducts to products such as [UO 2 (O)(NO 3 )] − spontaneously rearrange to create dihydroxides and that addition of O 2 is favored over addition of H 2 O to formally U(V) species.