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Generation of gas-phase VO2+, VOOH+, and VO2+-nitrile complex ions by electrospray ionization and collision-induced dissociation

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dc.contributor Wichita State University. Department of Chemistry en_US
dc.contributor.author Parsons, Zack en_US
dc.contributor.author Leavitt, Christopher M. en_US
dc.contributor.author Duong, Thanh en_US
dc.contributor.author Groenewold, Gary S. en_US
dc.contributor.author Gresham, Garold L. en_US
dc.contributor.author Van Stipdonk, Michael J. en_US
dc.date.accessioned 2012-02-06T17:15:22Z
dc.date.available 2012-02-06T17:15:22Z
dc.date.issued 2006-10-19 en_US
dc.identifier 17034156 en_US
dc.identifier 9890903 en_US
dc.identifier.citation The journal of physical chemistry. A. 2006 Oct 19; 110(41): 11627-35. en_US
dc.identifier.issn 1089-5639 en_US
dc.identifier.uri http://dx.doi.org/10.1021/jp062769p en_US
dc.identifier.uri http://hdl.handle.net/10057/4232
dc.description Click on the DOI link below to access the article (may not be free). en_US
dc.description.abstract Cationic metal species normally function as Lewis acids, accepting electron density from bound electron-donating ligands, but they can be induced to function as electron donors relative to dioxygen by careful control of the oxidation state and ligand field. In this study, cationic vanadium(IV) oxohydroxy complexes were induced to function as Lewis bases, as demonstrated by addition of O2 to an undercoordinated metal center. Gas-phase complex ions containing the vanadyl (VO2+), vanadyl hydroxide (VOOH+), or vanadium(V) dioxo (VO2+) cation and nitrile (acetonitrile, propionitrile, butyronitrile, or benzonitrile) ligands were generated by electrospray ionization (ESI) for study by multiple-stage tandem mass spectrometry. The principal species generated by ESI were complexes with the formula [VO(L)n]2+, where L represents the respective nitrile ligands and n=4 and 5. Collision-induced dissociation (CID) of [VO(L)5]2+ eliminated a single nitrile ligand to produce [VO(L)4]2+. Two distinct fragmentation pathways were observed for the subsequent dissociation of [VO(L)4]2+. The first involved the elimination of a second nitrile ligand to generate [VO(L)3]2+, which then added neutral H2O via an association reaction that occurred for all undercoordinated vanadium complexes. The second [UO(L)4]2+ fragmentation pathway led instead to the formation of [VOOH(L)2]+ through collisions with gas-phase H2O and concomitant losses of L and [L+H]+. CID of [VOOH(L)2]+ caused the elimination of a single nitrile ligand to generate [VOOH(L)]+, which rapidly added O2 (in addition to H2O) by a gas-phase association reaction. CID of [VONO3(L)2]+, generated from spray solutions created by mixing VOSO4 and Ba(NO3)2 (and precipitation of BaSO4), caused elimination of NO2 to produce [VO2(L)2]+. CID of [VO2(L)2]+ produced elimination of a single nitrile ligand to form [VO2(L)]+, a V(V) analogue to the O2-reactive V(IV) species [VOOH(L)]+; however, this V(V) complex was unreactive with O2, which indicates the requirement for an unpaired electron in the metal valence shell for O2 addition. In general, the [VO2(L)2]+ species required higher collisions energies to liberate the nitrile ligand, suggesting that they are more strongly bound than the [VOOH(L)2]+ counterparts. en_US
dc.format.extent 11627-35 en_US
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.relation.ispartofseries The journal of physical chemistry. A en_US
dc.relation.ispartofseries J Phys Chem A en_US
dc.source NLM en_US
dc.subject Research Support, Non-U.S. Gov't en_US
dc.subject Research Support, U.S. Gov't, Non-P.H.S. en_US
dc.subject.mesh Nitriles/chemistry en_US
dc.subject.mesh Spectrometry, Mass, Electrospray Ionization en_US
dc.subject.mesh Tandem Mass Spectrometry en_US
dc.subject.mesh Vanadates/chemistry en_US
dc.title Generation of gas-phase VO2+, VOOH+, and VO2+-nitrile complex ions by electrospray ionization and collision-induced dissociation en_US
dc.type Article en_US
dc.coverage.spacial United States en_US
dc.description.version peer reviewed en_US
dc.rights.holder Copyright © 2006 American Chemical Society en_US

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