Intrinsic reactivity of [OUCH]+: Apparent synthesis of [OUS]+ by reaction with CS2

• Published in: Rapid communications in mass spectrometry Vol. 36; no. 8; pp. e9260 - n/a
• Main Authors: Metzler, Luke J., Farmen, Christopher T., Fry, Allison N., Seibert, Mark P., Massari, Kayla A., Corcovilos, Theodore A., Stipdonk, Michael J.
• Format: Journal Article
• Language: English
• Published: 30-04-2022
• ISSN: 0951-4198; 1097-0231
• DOI: 10.1002/rcm.9260

Rationale
Building on our report that collision‐induced dissociation (CID) can be used to create the highly reactive U‐alkylidyne species [O=U≡CH]+, our goal was to determine whether the species could be as an intermediate for synthesis of [OUS]+ by reaction with carbon disulfide (CS2).
Methods
Cationic uranyl‐propiolate precursor ions were generated by electrospray ionization, and multiple‐stage CID in a linear trap instrument was used to prepare [O=U≡CH]+. Neutral CS2 was admitted into the trap through a modified He inlet and precision leak valves.
Results
The [O=U≡CH]+ ion reacts with CS2 to generate [OUS]+. CID of [OUS]+ causes elimination of the axial sulfide ligand to generate [OU]+. Using isotopically labeled reagent, we found that [OUS]+ reacts with O2 to create [UO2]+.
Conclusions
[O=U≡CH]+ proves to be a useful reagent ion for synthesis of [OUS]+, a species that to date has only been created by gas‐phase reactions of U+ and U2+. Dissociation of [OUS]+ to create [OU]+, but not [US]+, and the efficient conversion of the species into [UO2]+, is consistent with the relative differences in U–O and U–S bond energies.