title: Reactions of CH(3)CHO(.+) and of CH(3)COH(.+) with water upon Fourier transform ion cyclotron resonance conditions.
abstract: The reactions of CH(3)CHO(+) and of CH(3)COH(+) with water yield the same products, at almost the same rate. It is shown, by using a characteristic reaction of the carbene structure, that a molecule of water converts CH(3)COH(+) into its more stable isomer CH(3)CHO(+), which is a new example of catalyzed 1,2-H transfer. The dominant product is the proton-bound dimer of water which, in fact, comes from the [H(2)OH(+)...CH(3)(.)] and [H(2)OH(+)...CO] primary products whose observed abundances are poor. In a related system, ionized formamide/water, a water molecule catalyzes the 1,3-transfer leading from the solvated carbene to the [H(2)O...H(+)...H(2)N-C=O)] stable intermediate, which eliminates CO without back energy. In contrast, such a process does not take place in the studied system since the cleavage of the so formed [H(2)OH(+)...CH(3)CO] transient intermediate involves a high back energy; this is explained by the charge repartition within this intermediate. In fact, a different pathway takes place. The solvated acetaldehyde ion isomerizes into a terbody intermediate in which protonated water is bonded to a CO molecule on the one hand and to a methyl radical on the other hand. Simple cleavages of this complex yield the observed products.
authors.affiliation: Laboratoire des Mécanismes Réactionnels, UMR CNRS, Ecole Polytechnique, F-91128, Palaiseau, France.
authors.forename: H
authors.initials: H
authors.lastname: Nedev
authors.forename: G
authors.initials: G
authors.lastname: Van Der Rest
authors.forename: P
authors.initials: P
authors.lastname: Mourgues
authors.forename: H E
authors.initials: HE
authors.lastname: Audier