Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration

Büker H-H, Grützmacher H-F, Crestoni ME, Ricci A (1997)
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES 160(1-3): 167-181.

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Abstract
The differences in the gas-phase basicities (GBs) of isomers can be used for a semi-quantitative mixture analysis. For this ''gas-phase titration'' method, the mixture of isomers is completely protonated in the external ion source of a FT-ion cyclotron resonance spectrometry (ICR) spectrometer and undergoes selective, stepwise deprotonation by reactions with appropriate bases within the FT-ICR cell. This method is demonstrated by the analysis of a mixture of three isomeric alkylpyridines differing in GB by 4 kJ mol(-1). ''Gas-phase titration'' is employed to detect the isomerization of gaseous para-xylenium ions XpH+ into the more stable ortho and meta isomers XoH+ and XmH+ by 1,2-methyl shifts around the aromatic ring. Strongly exoenergetic protonation of para-xylene X-p in the external ion source by chemical ionization (CI) (methane) and gas-phase titration of the resulting XH+ after transfer into the FT-ICR cell reveals isomerization of XpH+ into a mixture of less than or equal to 15 mol% XpH+, 25 +/- 3 mol% XoH+, and 60 +/- 4 mol% XmH+. The degree of isomerization depends clearly on the exoenergicity of the initial protonation and is significantly reduced for XH+ ions generated by CI (dimethyl ether). This effect is confirmed by an investigation of the controlled protonation of X-p by selected proton donors AH(+) (A = C2H5CN, CH3OH, C6H6, C3H6, H2O, C2H4) in the FT-ICR cell. This study shows that the chemical nature of A is also important for the degree of isomerization. The results are explained convincingly by assuming isomerization of the XpH+ ions through multiple 1,2-methyl shifts within a long lived ion/ molecule complex [A ... H+Xp], formed by proton transfer from AH(+) to X-p. The rearrangement is driven by the excess energy of the complex as a result of exothermic proton transfer and electrostatic activation of the complex, and competes with the dissociation of the excited complex. (C) 1997 Elsevier Science B.V.
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Büker H-H, Grützmacher H-F, Crestoni ME, Ricci A. Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES. 1997;160(1-3):167-181.
Büker, H. - H., Grützmacher, H. - F., Crestoni, M. E., & Ricci, A. (1997). Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 160(1-3), 167-181.
Büker, H. - H., Grützmacher, H. - F., Crestoni, M. E., and Ricci, A. (1997). Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES 160, 167-181.
Büker, H.-H., et al., 1997. Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 160(1-3), p 167-181.
H.-H. Büker, et al., “Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration”, INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, vol. 160, 1997, pp. 167-181.
Büker, H.-H., Grützmacher, H.-F., Crestoni, M.E., Ricci, A.: Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES. 160, 167-181 (1997).
Büker, Heinz-Hermann, Grützmacher, Hans-Friedrich, Crestoni, Maria Elisa, and Ricci, Andreina. “Proton induced methyl group shifts in gaseous xylenium ions. Distinguishing isomers by gas-phase titration”. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES 160.1-3 (1997): 167-181.
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