Mechanistic Analysis of Nucleophilic Substrates Oxidation by Functional Models of Vanadium-Dependent Haloperoxidases: A Density Functional Theory Study (Eur. J. Inorg. Chem. 4/2007)

Abstract

The cover picture shows four substrates (Cl – , Br – , I – , and dimethyl sulfide) that all pass through nearly identical transition states when oxidized by (hydroperoxido)(oxido)vanadium(V) 2,2′-[(2-hydroxyethyl)imino]diacetate [VO(OOH)Hheida]. The differences in the physical properties of the substrate are represented by the changes in the color scheme for each panel. Despite the different “colors”, certain features of the transition states are always maintained, such as: nearly linear substrate peroxo oxygen bond angles, nucleophilic attack of the substrate on the unprotonated peroxo oxygen atom, and nearly complete hydroperoxo oxygen bond. This work lays the foundation for the development of more effective and potentially stereoselective catalysts based on the biomimetic catalyst V(OOH)Hheida. Details of this computational study can be found in the article by V. L. Pecoraro, and L. De Gioia on p. 515 ff.