1. Gas-Phase Deconstruction of UO22+: Mass Spectrometry Evidence for Generation of [OUVICH]+ by Collision-Induced Dissociation of [UVIO2(C≡CH)]+
- Author
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Luke J. Metzler, Mary C. Sherman, Irena Tatosian, Anna Iacovino, Amanda R. Bubas, Michael J. Van Stipdonk, and Árpád Somogyi
- Subjects
Collision-induced dissociation ,Orbital hybridisation ,Chemistry ,Decarboxylation ,010401 analytical chemistry ,010402 general chemistry ,Triple bond ,Mass spectrometry ,01 natural sciences ,Dissociation (chemistry) ,0104 chemical sciences ,Ion ,Crystallography ,Structural Biology ,Density functional theory ,Spectroscopy - Abstract
Because of the high stability and inertness of the U=O bonds, activation and/or functionalization of UO22+ and UO2+ remain challenging tasks. We show here that collision-induced dissociation (CID) of the uranyl-propiolate cation, [UVIO2(O2C-C≡CH)]+, can be used to prepare [UVIO2(C≡CH)]+ in the gas phase by decarboxylation. Remarkably, CID of [UVIO2(C≡CH)]+ caused elimination of CO to create [OUVICH]+, thus providing a new example of a well-defined substitution of an “yl” oxo ligand of UVIO22+ in a unimolecular reaction. Relative energies for candidate structures based on density functional theory calculations suggest that the [OUVICH]+ ion is a uranium-methylidyne product, with a U≡C triple bond composed of one σ-bond with contributions from the U df and C sp hybrid orbitals, and two π-bonds with contributions from the U df and C p orbitals. Upon isolation, without imposed collisional activation, [OUVICH]+ appears to react spontaneously with O2 to produce [UVO2]+.
- Published
- 2019
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