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Collision‐induced dissociation of uranyl‐methoxide and uranyl‐ethoxide cations: Formation of UO 2 H + and uranyl‐alkyl product ions
Author(s) -
Van Stipdonk Michael J.,
Hanley Cassandra,
Perez Evan,
Pestok Jordan,
Mihm Patricia,
Corcovilos Theodore A.
Publication year - 2016
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.7668
Subject(s) - chemistry , uranyl , dissociation (chemistry) , alkoxide , collision induced dissociation , methoxide , tandem mass spectrometry , mass spectrometry , alkyl , fragmentation (computing) , electrospray ionization , ion , methanol , medicinal chemistry , alcohol , organic chemistry , chromatography , catalysis , computer science , operating system
Rationale The lower levels of adventitious H 2 O in a linear ion trap allow the fragmentation reactions of [UO 2 OCH 3 ] + and [UO 2 OCH 2 CH 3 ] + to be examined in detail. Methods Methanol‐ and ethanol‐coordinated UO 2 2+ ‐alkoxide precursors were generated by electrospray ionization (ESI). Multiple‐stage tandem mass spectrometry (MS n ) and collision‐induced dissociation (CID) were performed using a linear ion trap mass spectrometer. Results CID of [UO 2 OCH 3 (CH 3 OH) n ] + and [UO 2 OCH 2 CH 3 (CH 3 CH 2 OH) n ] + , n = 3 and 2, causes loss of neutral alcohol ligands, leading ultimately to bare uranyl‐alkoxide species. Comparison of ‘native’ to deuterium‐labeled precursors reveals dissociation pathways not previously observed in 3‐D ion trap experiments. Conclusions UO 2 H + is generated from [UO 2 OCH 3 ] + by transfer of H from the methyl group. Variable‐energy and variable‐time CID experiments suggest that the apparent threshold for production of UO 2 H + is lower than for UO 2 + , but the pathway is kinetically less favored for the former than for the latter. CID experiments reveal that [UO 2 OCH 2 CH 3 ] + dissociates to generate [UO 2 CH 3 ] + , a relatively rare species with a U–C bond, and [UO 2 (O = CH 2 )] + .