A density functional theory investigation of the bromide oxidation mechanism by a vanadium bromoperoxidase model complex

Abstract  

Density functional theory has been used to study the mechanism of bromide oxidation by the oxo-peroxo complex K[VO(O₂)Hheida] (heida = N-(2-hydroxyethyl)iminodiacetic acid), which has the highest reported rate constant for bromide oxidation of any vanadium complex. Two possible mechanisms were explored, involving bromide attack on a protonated or unprotonated peroxo atom. The direct nucleophilic attack of bromide on a protonated peroxo begins the reaction, i.e. the protonated peroxo ligand is the active site of reaction. We examined five different transition states in the mechanism. Two transition states were found to have lower activation barriers. A reduction in the potential energy barriers, when calculated using the polarisable continuum model, indicates that with the involvement of acetonitrile as a solvent the transition states become more stable.