Oxygen atom transfer to positive ions: A novel reaction of ozone in the gas phase

Maria Mendes, Luiz Moraes, Regina Sparrapan, Marcos Eberlin, Risto Kostiainen, Tapio Kotiaho

Research output: Contribution to journalArticleScientificpeer-review

17 Citations (Scopus)

Abstract

In the gas phase, neutral ozone (O3) transfers an oxygen atom to several positive ions, i.e. the radical cations of pyridines (R−Py+•; R = H, CH3, C2H5, and Cl), pyrimidine (Pi+•), and alkyl halides (CH3X+•; X = Cl and I), and the halogen cations (X+; X = Cl, Br, and I). Reactivity changes drastically within the halogen series (Cl+ ≪ Br+ ≤ I+), whereas no O-transfer occurs to F+.
The oxide derivatives R−Py+−O•, Pi+−O•, CH3X+−O•, and XO+ are formed, as demonstrated by pentaquadrupole (QqQqQ) double- and triple-stage mass spectrometry. No oxygen atom transfer occurs, however, in “inverse” reactions, i.e., those of ionized ozone (O3+•) with the corresponding neutrals; and charge transfer dominates.
Ab initio calculations suggest that O-transfer from ozone to ionized pyridine yields ionized pyridine N-oxide via simple nucleophilic addition of ozone as opposed to 1,3-dipolar cycloaddition. Similar nucleophilic addition followed by O2 loss is also the most likely mechanism for O-transfer from ozone to the ionized alkyl halides and halogen cations.
This novel O-transfer reaction to positive ions, which expands our knowledge of the rich chemistry of ozone, introduces a new pathway for the gas-phase oxidation of halogen atoms, pyridines, pyrimidines, alkyl halides, and analogues, and consequently for the gas-phase generation of their chemically interesting but difficult to access ionized oxides.
Original languageEnglish
Pages (from-to)7869-7874
JournalJournal of the American Chemical Society
Volume120
Issue number31
DOIs
Publication statusPublished - 1998
MoE publication typeA1 Journal article-refereed

Fingerprint

Ozone
Halogens
Gases
Positive ions
Ions
Oxygen
Pyridine
Atoms
Pyridines
Cations
Oxides
Pyrimidines
Cycloaddition
Cycloaddition Reaction
Mass spectrometry
Charge transfer
Mass Spectrometry
Derivatives
Oxidation

Cite this

Mendes, M., Moraes, L., Sparrapan, R., Eberlin, M., Kostiainen, R., & Kotiaho, T. (1998). Oxygen atom transfer to positive ions: A novel reaction of ozone in the gas phase. Journal of the American Chemical Society, 120(31), 7869-7874. https://doi.org/10.1021/ja971251j
Mendes, Maria ; Moraes, Luiz ; Sparrapan, Regina ; Eberlin, Marcos ; Kostiainen, Risto ; Kotiaho, Tapio. / Oxygen atom transfer to positive ions : A novel reaction of ozone in the gas phase. In: Journal of the American Chemical Society. 1998 ; Vol. 120, No. 31. pp. 7869-7874.
@article{dcf05a1c314e46f88f88090aec92bade,
title = "Oxygen atom transfer to positive ions: A novel reaction of ozone in the gas phase",
abstract = "In the gas phase, neutral ozone (O3) transfers an oxygen atom to several positive ions, i.e. the radical cations of pyridines (R−Py+•; R = H, CH3, C2H5, and Cl), pyrimidine (Pi+•), and alkyl halides (CH3X+•; X = Cl and I), and the halogen cations (X+; X = Cl, Br, and I). Reactivity changes drastically within the halogen series (Cl+ ≪ Br+ ≤ I+), whereas no O-transfer occurs to F+. The oxide derivatives R−Py+−O•, Pi+−O•, CH3X+−O•, and XO+ are formed, as demonstrated by pentaquadrupole (QqQqQ) double- and triple-stage mass spectrometry. No oxygen atom transfer occurs, however, in “inverse” reactions, i.e., those of ionized ozone (O3+•) with the corresponding neutrals; and charge transfer dominates. Ab initio calculations suggest that O-transfer from ozone to ionized pyridine yields ionized pyridine N-oxide via simple nucleophilic addition of ozone as opposed to 1,3-dipolar cycloaddition. Similar nucleophilic addition followed by O2 loss is also the most likely mechanism for O-transfer from ozone to the ionized alkyl halides and halogen cations. This novel O-transfer reaction to positive ions, which expands our knowledge of the rich chemistry of ozone, introduces a new pathway for the gas-phase oxidation of halogen atoms, pyridines, pyrimidines, alkyl halides, and analogues, and consequently for the gas-phase generation of their chemically interesting but difficult to access ionized oxides.",
author = "Maria Mendes and Luiz Moraes and Regina Sparrapan and Marcos Eberlin and Risto Kostiainen and Tapio Kotiaho",
year = "1998",
doi = "10.1021/ja971251j",
language = "English",
volume = "120",
pages = "7869--7874",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society ACS",
number = "31",

}

Mendes, M, Moraes, L, Sparrapan, R, Eberlin, M, Kostiainen, R & Kotiaho, T 1998, 'Oxygen atom transfer to positive ions: A novel reaction of ozone in the gas phase', Journal of the American Chemical Society, vol. 120, no. 31, pp. 7869-7874. https://doi.org/10.1021/ja971251j

Oxygen atom transfer to positive ions : A novel reaction of ozone in the gas phase. / Mendes, Maria; Moraes, Luiz; Sparrapan, Regina; Eberlin, Marcos; Kostiainen, Risto; Kotiaho, Tapio.

In: Journal of the American Chemical Society, Vol. 120, No. 31, 1998, p. 7869-7874.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Oxygen atom transfer to positive ions

T2 - A novel reaction of ozone in the gas phase

AU - Mendes, Maria

AU - Moraes, Luiz

AU - Sparrapan, Regina

AU - Eberlin, Marcos

AU - Kostiainen, Risto

AU - Kotiaho, Tapio

PY - 1998

Y1 - 1998

N2 - In the gas phase, neutral ozone (O3) transfers an oxygen atom to several positive ions, i.e. the radical cations of pyridines (R−Py+•; R = H, CH3, C2H5, and Cl), pyrimidine (Pi+•), and alkyl halides (CH3X+•; X = Cl and I), and the halogen cations (X+; X = Cl, Br, and I). Reactivity changes drastically within the halogen series (Cl+ ≪ Br+ ≤ I+), whereas no O-transfer occurs to F+. The oxide derivatives R−Py+−O•, Pi+−O•, CH3X+−O•, and XO+ are formed, as demonstrated by pentaquadrupole (QqQqQ) double- and triple-stage mass spectrometry. No oxygen atom transfer occurs, however, in “inverse” reactions, i.e., those of ionized ozone (O3+•) with the corresponding neutrals; and charge transfer dominates. Ab initio calculations suggest that O-transfer from ozone to ionized pyridine yields ionized pyridine N-oxide via simple nucleophilic addition of ozone as opposed to 1,3-dipolar cycloaddition. Similar nucleophilic addition followed by O2 loss is also the most likely mechanism for O-transfer from ozone to the ionized alkyl halides and halogen cations. This novel O-transfer reaction to positive ions, which expands our knowledge of the rich chemistry of ozone, introduces a new pathway for the gas-phase oxidation of halogen atoms, pyridines, pyrimidines, alkyl halides, and analogues, and consequently for the gas-phase generation of their chemically interesting but difficult to access ionized oxides.

AB - In the gas phase, neutral ozone (O3) transfers an oxygen atom to several positive ions, i.e. the radical cations of pyridines (R−Py+•; R = H, CH3, C2H5, and Cl), pyrimidine (Pi+•), and alkyl halides (CH3X+•; X = Cl and I), and the halogen cations (X+; X = Cl, Br, and I). Reactivity changes drastically within the halogen series (Cl+ ≪ Br+ ≤ I+), whereas no O-transfer occurs to F+. The oxide derivatives R−Py+−O•, Pi+−O•, CH3X+−O•, and XO+ are formed, as demonstrated by pentaquadrupole (QqQqQ) double- and triple-stage mass spectrometry. No oxygen atom transfer occurs, however, in “inverse” reactions, i.e., those of ionized ozone (O3+•) with the corresponding neutrals; and charge transfer dominates. Ab initio calculations suggest that O-transfer from ozone to ionized pyridine yields ionized pyridine N-oxide via simple nucleophilic addition of ozone as opposed to 1,3-dipolar cycloaddition. Similar nucleophilic addition followed by O2 loss is also the most likely mechanism for O-transfer from ozone to the ionized alkyl halides and halogen cations. This novel O-transfer reaction to positive ions, which expands our knowledge of the rich chemistry of ozone, introduces a new pathway for the gas-phase oxidation of halogen atoms, pyridines, pyrimidines, alkyl halides, and analogues, and consequently for the gas-phase generation of their chemically interesting but difficult to access ionized oxides.

U2 - 10.1021/ja971251j

DO - 10.1021/ja971251j

M3 - Article

VL - 120

SP - 7869

EP - 7874

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 31

ER -