Experimental and Theoretical Studies on the Fragmentation of Gas-Phase Uranyl鈥? Neptunyl鈥? and Plutonyl鈥揇iglycolamide Complexes
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- 作者：Yu Gong ; Han-Shi Hu ; Linfeng Rao ; Jun Li ; John K. Gibson
- 刊名：Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：October 10, 2013
- 年：2013
- 卷：117
- 期：40
- 页码：10544-10550
- 全文大小：299K
- 年卷期：v.117,no.40(October 10, 2013)
- ISSN：1520-5215
文摘
Fragmentation of actinyl(VI) complexes UVIO2(L)22+, NpVIO2(L)22+, and PuVIO2(L)22+ (L = tetramethyl-3-oxa-glutaramide, TMOGA) produced by electrospray ionization was examined in the gas phase by collision induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Cleavage of the C鈥揙ether bond was observed for all three complexes, with dominant products being UVIO2(L)(L-86)+ with charge reduction, and NpVIO2(L)(L-101)2+ and PuVIO2(L)(L-101)2+ with charge conservation. The neptunyl and plutonyl complexes also exhibited substantial L+ loss to give pentavalent complexes NpVO2(L)+ and PuVO2(L)+, whereas the uranyl complex did not, consistent with the comparative An 5f-orbital energies and the AnVIO22+/AnVO2+ (An = U, Np, Pu) reduction potentials. CID of NpVO2(L)2+ and PuVO2(L)2+ was dominated by neutral ligand loss to form NpVO2(L)+ and PuVO2(L)+, which hydrated by addition of residual water in the ion trap; UVO2(L)2+ was not observed. Theoretical calculations of the structures and bonding of the AnVIO2(L)22+ complexes using density functional theory reveal that the metal centers are coordinated by six oxygen atoms from two TMOGA ligands.