A novel 'thermodynamic' mechanistic rationale of haloperoxidase cataly
sis is based on the following two assumptions: (i) the role of enzyme
consists only in the rapid equilibration between the halogen-containin
g species originating from halide and hydrogen peroxide; (ii) the inte
raction between the enzyme and organic substrate is kinetically insign
ificant and halogenation occurs as a result of the electrophilic attac
k of the active brominating (Br-3(-), Br-2 and HBrO) or chlorinating (
HClO) species at monochlorodimedon indicative of a higher chloride 'sp
ecificity' of chloroperoxidase from C. fumago.