title: Chemically triggered C-ON bond homolysis in alkoxyamines. 6. Effect of the counteranion.
abstract: We showed (J. Org. Chem. 2012, 77, 9634) that the activation by methylation of pyridyl-based alkoxyamine 1 increased with the hydrogen bond donor properties of solvents. In this paper, activation of 1 by protonation with acids, CF3COOH and CSA, in tert-butylbenzene (t-BuPh) and in H2O/MeOH afforded, with CF3COOH, k(d) 28-fold larger in H2O/MeOH than in t-BuPh, whereas it was only 4-fold larger when CSA was used. This puzzling observation was ascribed to the dissociation of the intimate ion pair.
authors.affiliation: Aix-Marseille Université, CNRS, ICR UMR-7273, case 551, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France.
authors.forename: Gérard
authors.initials: G
authors.lastname: Audran
authors.forename: Paul
authors.initials: P
authors.lastname: Brémond
authors.forename: Sylvain R A
authors.initials: SR
authors.lastname: Marque
authors.forename: Germain
authors.initials: G
authors.lastname: Obame
mesh_terms: D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D006860:Hydrogen Bonding; D015394:Molecular Structure
chemical_list: D000588:Amines; D000838:Anions