Show simple item record

dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorParsons, Zacken_US
dc.contributor.authorLeavitt, Christopher M.en_US
dc.contributor.authorDuong, Thanhen_US
dc.contributor.authorGroenewold, Gary S.en_US
dc.contributor.authorGresham, Garold L.en_US
dc.contributor.authorVan Stipdonk, Michael J.en_US
dc.identifier.citationThe journal of physical chemistry. A. 2006 Oct 19; 110(41): 11627-35.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractCationic 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.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesThe journal of physical chemistry. Aen_US
dc.relation.ispartofseriesJ Phys Chem Aen_US
dc.subjectResearch Support, Non-U.S. Gov'ten_US
dc.subjectResearch Support, U.S. Gov't, Non-P.H.S.en_US
dc.subject.meshSpectrometry, Mass, Electrospray Ionizationen_US
dc.subject.meshTandem Mass Spectrometryen_US
dc.titleGeneration of gas-phase VO2+, VOOH+, and VO2+-nitrile complex ions by electrospray ionization and collision-induced dissociationen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2006 American Chemical Societyen_US

Files in this item


There are no files associated with this item.

This item appears in the following Collection(s)

Show simple item record