Electron impact studies CX—+<i>E</i> spectra from negative ions. <i>Ortho</i> effects and skeletal rearrangement reactions from sulphur compounds

Bowie, John H.; White, P. Y.; Wilson, Joe C.; Larsson, F. C. V.; Lawesson, S.‐O.; Madsen, Jacob; Nolde, C.; Schroll, Gustav

doi:10.1002/oms.1210120402

Cited by 22 publications

(9 citation statements)

References 30 publications

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“…But in the case of p-nitrophenyl phenyl sulfone, in which similar rearrangements occur in both the positive and negative molecular ions, the rearrangements found in the positive ion spectrum also appear in the charge inversion spectrum. The anion must have rearranged before the collision process Ortho effects produce abundant ions in the charge inversion spectra of 2-(0-nitrophenyl)-1,3-dithiane, 2-methylsulfinylaniline, and 2-methoxysulfinylaniline (72). Either rearrangements with a higher rate than those noted in the preceding paragraph or a population including rearranged ions is present.…”

Section: Sulfur Compoundsmentioning

confidence: 94%

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Charge inversion of negative ions in tandem instruments

Bursey

1990

Mass Spectrometry Reviews

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Section: Sulfur Compoundsmentioning

confidence: 94%

“…Either rearrangements with a higher rate than those noted in the preceding paragraph or a population including rearranged ions is present. (72).…”

Section: Sulfur Compoundsmentioning

confidence: 99%

Charge inversion of negative ions in tandem instruments

Bursey

1990

Mass Spectrometry Reviews

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“…4). seem to be relatively rare, and we estimate that 12 3 fragmentation takes place within 108sec of the collision process (26). Let us consider a particular example where a charge inversion spectrum confirms the structure of a negative ion produced by a rearrangement process.…”

Section: Collisional Processes Of Negative Ionsmentioning

confidence: 98%

“…The pioneering work of Cooks and Beynon (7) since this spectrum, at a given accelerating potential, is independent of the pressure of the collision (91) gas provided the pressure in the collision region is (69) (108) less than 3 x 10-torr (26). As an illustration of (45) this feature, the o-and p-isomers of MeC6H4S-(39) (Sl) (65 give reproducible, but different charge inversion (27) 1 |l (63) (77)4 (82) (121) spectra (26) (see Fig.…”

Section: Collisional Processes Of Negative Ionsmentioning

confidence: 99%

“…formed within 1012sec, of the collision process are generally not stable, and peaks due to these species are either not detected, or alternatively are observed in small abundance. Ions A' are generally formed in electronically excited states, and fragment in less than 108sec to produce an intense spectrum of fragment positive ions (24)(25)(26)(27)(28).…”

Section: Collisional Processes Of Negative Ionsmentioning

confidence: 99%

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Recent Advances in Negative Ion Mass Spectrometry

Bowie¹

1980

Environmental Health Perspectives

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The paper describes theoretical and applied applications of negative ion chemistry carried out at Adelaide during the past five years. Kinetic energy release in negative metastable ion decompositions is described, with particular reference to simple cleavage reactions, rearrangement reactions, and reactions which proceed by dual mechanisms. The application of deuterium isotope effects as a mechanistic probe is illustrated by reference to the elimination of ketene from quinone acetate negative ions.Charge stripping of a negative ion yields a decomposing positive ion, which produces a dissociative charge inversion spectrum of the negative ion. This technique allows the study of positive ions not available by conventional ionization; it provides a fingerprint for the parent positive ion produced in the collision process, and it may be used to determine the structure of the precursor negative ion. Finally, a combination of a negative ion spectrum and a charge inversion spectrum may be used as an analytical technique for the structure determination of unknown molecules.

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Charge inversion mass spectrometry: dissociation of resonantly neutralized molecules

Hayakawa

2004

J. Mass Spectrom.

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Charge inversion mass spectrometry is an MS/MS method in which the electric charge of the precursor ions is opposite to that of the secondary product ions. Charge inversion mass spectrometry is classified into four types depending on the electric charge and time scale of collisions. Charge inversion mass spectrometry using collisions with gaseous targets in the keV energy collision range has provided insights into the structures and reactions of ions and neutral molecules. The characteristics of charge inversion experiments are presented in terms of the reaction endothermicities and the cross sections and their dependence on the target species. In the case of rare-gas or simple molecular targets, double-electron transfer in one collision is effective to form positive ions from negative ions, while, in the case of alkali metal targets, successive single-electron transfers in two collisions is effective to form negative ions from positive ions. On the basis of the observed target-density dependence of the product ion intensity and thermochemical considerations for internal energy distribution using thermometer molecules, the charge inversion processes using alkali metal targets have been confirmed to occur by electron transfers in successive collisions and the dissociation processes are found to occur in energy-selected neutral species formed from near-resonant neutralization with alkali metal targets. While collisionally activated dissociation (CAD) is due to dissociation of activated ions with broad internal energy distributions, the charge inversion process using alkali metal targets is due to dissociation of energy-selected neutral species with narrow internal energy distributions. The charge inversion/alkali metal spectra provide clear differentiation of the isomeric cations of C(2)H(2), C(3)H(4) and dichlorobenzenes. The CAD spectra of these isomeric cations are similar.

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Electron impact studies CX—+E spectra from negative ions. Ortho effects and skeletal rearrangement reactions from sulphur compounds

Cited by 22 publications

References 30 publications

Charge inversion of negative ions in tandem instruments

Charge inversion of negative ions in tandem instruments

Recent Advances in Negative Ion Mass Spectrometry

Charge inversion mass spectrometry: dissociation of resonantly neutralized molecules

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