TY - JOUR
T1 - Oxidation of 2-propanol ligands during collision-induced dissociation of a gas-phase uranyl complex
AU - Van Stipdonk, Michael J.
AU - Chien, Winnie
AU - Anbalagan, Victor
AU - Gresham, Garold L.
AU - Groenewold, Gary S.
N1 - Funding Information:
M.V.S. acknowledges support for this work by a grant from the National Science Foundation (CAREER-0239800), a First Award from the Kansas Technology Enterprise Corporation/Kansas NSF EPSCoR program and a subcontract from the US Department of Energy through the INEEL Institute. G.S.G. acknowledges support by the US Department of Energy, Environmental Systems Research Program, under contract DE-AC-07-99ID13727. Funds for the purchase of the LCQ-Deca instrument were provided by the Kansas NSF EPSCoR program and the Wichita State University College of Liberal Arts and Sciences.
PY - 2004/10/1
Y1 - 2004/10/1
N2 - We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO 2OCH(CH 3) 2)(HOCH(CH 3) 2)] +, derived from dissociation of the gas-phase precursor [(UO 2NO 3)(HOCH(CH 3) 2) 3] + eliminates two H atoms and CH 3 in consecutive stages to generate a monopositive complex composed of the U(V) species UO2+ coordinated by acetone and acetaldehyde, i.e. [UO2+(OC(CH 3) 2)(OC(H)CH 3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave UO2+. Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni 2+, Co 2+, Pb 2+ and Ca 2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.
AB - We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO 2OCH(CH 3) 2)(HOCH(CH 3) 2)] +, derived from dissociation of the gas-phase precursor [(UO 2NO 3)(HOCH(CH 3) 2) 3] + eliminates two H atoms and CH 3 in consecutive stages to generate a monopositive complex composed of the U(V) species UO2+ coordinated by acetone and acetaldehyde, i.e. [UO2+(OC(CH 3) 2)(OC(H)CH 3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave UO2+. Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni 2+, Co 2+, Pb 2+ and Ca 2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.
KW - 2-Propanol oxidation
KW - Collision-induced-dissociation
KW - Electrospray ionization
KW - Tandem mass spectrometry
KW - Uranyl-ligand cations
UR - https://www.scopus.com/pages/publications/5344271158
U2 - 10.1016/j.ijms.2004.07.007
DO - 10.1016/j.ijms.2004.07.007
M3 - Article
AN - SCOPUS:5344271158
SN - 1387-3806
VL - 237
SP - 175
EP - 183
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
IS - 2-3
ER -