title: Nucleophilic substitution reactions of N-chloramines: evidence for a change in mechanism with increasing nucleophile reactivity.
abstract: Third-order rate constants (kNu)H (M-2 s-1) for the hydronium ion catalyzed reactions of a range of nucleophiles with N-chlorotaurine (1) in water at 25 degrees C and I=0.5 (NaClO4) are reported. The solvent deuterium isotope effects on hydronium ion catalysis of the reaction with 1 of bromide and iodide ion are (kBr)H/(kBr)D=0.30 and (kI)H/(kI)D=0.54, respectively. The inverse nature of these isotope effects and the absence of general acid catalysis are consistent with a stepwise mechanism involving protonation of 1 in a fast preequilibrium step. The appearance of strong catalysis by general acids for the reaction of the more nucleophilic SO(3)2- and HOCH2CH2S- with the chloramine indicates a change to a concerted mechanism, with protonation of the chloramine at nitrogen and chlorine transfer to the nucleophile occurring in a single step. A rough estimate of the lifetime of the protonated chloramine in the presence of the thiolate anion suggests that the concerted mechanism is enforced by the absence of a significant lifetime of the protonated substrate in contact with the nucleophile. Theoretical calculations provide evidence against an electron-transfer mechanism for chlorination of the nucleophiles by protonated 1.
authors.affiliation: Departamento de Química Física, Facultad de Química, Universidad de Santiago, 15782 Santiago de Compostela, Spain.
authors.forename: Paula
authors.initials: P
authors.lastname: Calvo
authors.forename: Juan
authors.initials: J
authors.lastname: Crugeiras
authors.forename: Ana
authors.initials: A
authors.lastname: Ríos
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ríos
mesh_terms: D002021:Buffers; D002700:Chloramines / Q000737:chemistry* / Q000494:pharmacology; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D011789:Quantum Theory; D013329:Structure-Activity Relationship
chemical_list: D002021:Buffers; D002700:Chloramines