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Electron transfer dissociation of dipositive uranyl and plutonyl coordination complexes
Author(s) -
Rios Daniel,
Rutkowski Philip X,
Shuh David K.,
Bray Travis H.,
Gibson John K.,
Van Stipdonk Michael J.
Publication year - 2011
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.2011
Subject(s) - chemistry , uranyl , dissociation (chemistry) , electron transfer dissociation , hydroxide , electron transfer , electrospray ionization , solvent , ion , polyoxometalate , ligand (biochemistry) , inorganic chemistry , photochemistry , mass spectrometry , tandem mass spectrometry , organic chemistry , chromatography , biochemistry , receptor , catalysis
Reported here is a comparison of electron transfer dissociation (ETD) and collision‐induced dissociation (CID) of solvent‐coordinated dipositive uranyl and plutonyl ions generated by electrospray ionization. Fundamental differences between the ETD and CID processes are apparent, as are differences between the intrinsic chemistries of uranyl and plutonyl. Reduction of both charge and oxidation state, which is inherent in ETD activation of [An VI O 2 (CH 3 COCH 3 ) 4 ] 2+ , [An VI O 2 (CH 3 CN) 4 ] 2 , [U VI O 2 (CH 3 COCH 3 ) 5 ] 2+ and [U VI O 2 (CH 3 CN) 5 ] 2+ (An = U or Pu), is accompanied by ligand loss. Resulting low‐coordinate uranyl(V) complexes add O 2 , whereas plutonyl(V) complexes do not. In contrast, CID of the same complexes generates predominantly doubly‐charged products through loss of coordinating ligands. Singly‐charged CID products of [U VI O 2 (CH 3 COCH 3 ) 4,5 ] 2+ , [U VI O 2 (CH 3 CN) 4,5 ] 2+ and [Pu VI O 2 (CH 3 CN) 4 ] 2+ retain the hexavalent metal oxidation state with the addition of hydroxide or acetone enolate anion ligands. However, CID of [Pu VI O 2 (CH 3 COCH 3 ) 4 ] 2+ generates monopositive plutonyl(V) complexes, reflecting relatively more facile reduction of Pu VI to Pu V . Copyright © 2011 John Wiley & Sons, Ltd.