title: Multiplicity of Reaction Pathways in the Processes of Oxygen Transfer to Secondary Amines by Mo(VI) and W(VI) Peroxo Complexes.
abstract: Oxidation of N,N-benzylmethylamine, N,N-benzylisopropylamine, and N,N-benzyl-tert-butylamine by both anionic and neutral Mo(VI) and W(VI) oxodiperoxo complexes yields the corresponding nitrones quantitatively. The oxidation reactions employing anionic oxidants were performed in CHCl(3) and follow second-order kinetics, first order with respect to the amine and to the oxidant. The data were rationalized on the basis of a rate-determining nucleophilic attack of the amine onto the peroxide oxygen of the oxidant, with a transition state in which N-O bond formation and O-O bond cleavage occur in a concerted way (electrophilic oxygen transfer mechanism). This attack yields the corresponding hydroxylamine, which then is furtherly oxidized to nitrone in a fast step. On the other hand, in the case of neutral oxidants (1)H-NMR data as well as kinetic data indicate that amine coordinates the metal center replacing the original ligand HMPA and yields a new peroxo complex. For N,N-benzyl-tert-butylamine such a complex was isolated and characterized. These new peroxo complexes can themselves behave as electrophilic oxidants, transferring oxygen to external amine molecules through the same pathway followed by anionic oxidants, or can yield the reaction product by intramolecular oxidation of the coordinate amine. Measurements of added HMPA effects on oxidation rate would seem more consistent with the electrophilic oxygen transfer mechanism.
authors.affiliation: Dipartimento di Scienze Chimiche, University of Catania, V. le A. Doria 6, I-95125 Catania, Italy, and Dipartimento di Chimica Organica, University of Palermo, Via Archirafi 26, I-90123 Palermo, Italy.
authors.forename: Francesco P.
authors.initials: FP
authors.lastname: Ballistreri
authors.forename: Elena G. M.
authors.initials: EG
authors.lastname: Barbuzzi
authors.forename: Gaetano A.
authors.initials: GA
authors.lastname: Tomaselli
authors.forename: Rosa M.
authors.initials: RM
authors.lastname: Toscano