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Article: A study of the isomerization and dissociation of formal [[acetone-methanol].sub.+.] ion-molecule complexes (1).
- Article from:
- Canadian Journal of Chemistry
- Article date:
- November 1, 2005
- Author:
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Introduction
Keto-enol isomerization is a well-known process in solution in which the keto species is readily isomerized by acid or base catalysis into the corresponding enol (1). In the gas phase, isolated ketone or aldehyde radical cations do not enolize spontaneously. High-energy barriers that exceed the ions' first dissociation threshold effectively prevent this reaction (2). For example, experiments and theoretical calculations show that the acetone radical cation in the gas phase is 58 kJ/mol (3, 4) less stable than its enol isomer, and the energy barrier for the required intra-ionic 1,3-H shift lies 74 kJ/mol higher than the dissociation threshold of the ...