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Gas‐phase Unimolecular Reactivity of C 3 H 7 O + Cations: a Combined Mass Spectrometric–Molecular Orbital Study
Author(s) -
Bouchoux G.,
PenaudBerruyer F.,
Audier H. E.,
Mourgues P.,
Tortajada J.
Publication year - 1997
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199702)32:2<188::aid-jms464>3.0.co;2-g
Subject(s) - chemistry , isomerization , fourier transform ion cyclotron resonance , protonation , dissociation (chemistry) , ion , ion cyclotron resonance , molecular orbital , deuterium , mass spectrometry , bond dissociation energy , computational chemistry , photochemistry , molecule , atomic physics , organic chemistry , cyclotron , physics , chromatography , catalysis
The unimolecular dissociations of the two isomeric ions [CH 3 CH 2 CHOH] + (1) and [CH 3 CH 2 OCH 2 ] + (2) were re‐examined. Molecular orbital calculations conducted at the MP2/6–31G*//HF/6–31G*+ZPE level were used to characterize the corresponding potential energy profile. The experimental data were completed by a Fourier transform ion cyclotron resonance spectrometric investigation on the system [CH 2 OH] + +C 2 H 4 and by a study of various metastable [C 3 H 7 O] + ions. The isomerization pathway of lowest energy connecting 1 and 2 involves two ion–neutral complexes between protonated formaldehyde and ethene. The isomerization 1 ‐ 2 is typically a complex mediated reaction since the key step consists simply of the reorientation of the two partners [CH 2 OH] + and C 2 H 4 inside the ion–neutral cage. The model is demonstrated to account for the H–D exchange observed during the dissociation of variously deuterated species. © 1997 by John Wiley & Sons, Ltd.