Abstract
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 language | English |
|---|---|
| Pages (from-to) | 7869-7874 |
| Journal | Journal of the American Chemical Society |
| Volume | 120 |
| Issue number | 31 |
| DOIs | |
| Publication status | Published - 1998 |
| MoE publication type | A1 Journal article-refereed |
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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 journal › Article › Scientific › peer-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 -