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.