A DFT study of the cis-dihydroxylation of nitroaromatic compounds catalyzed by nitrobenzene dioxygenase.

ABSTRACT: The mechanism of cis-dihydroxylation of nitrobenzene and 2-nitrotoluene catalyzed by nitrobenzene 1,2-dioxygenase (NBDO), a member of the naphthalene family of Rieske non-heme iron dioxygenases, was studied by means of the density functional theory method using four models of the enzyme active site. Different possible reaction pathways for the substrate dioxygenation initiated either by the Fe(III)-OOH or HO-Fe(V)═O attack on the aromatic ring were considered and the computed activation barriers compared with the Gibbs free energy of activation for the oxygen-oxygen cleavage leading to the formation of the iron(V)-oxo species from its ferric hydroperoxo precursor. The mechanism of the substrate cis-dihydroxylation leading to the formation of a cis-dihydrodiol was then investigated, and the

SUBMITTER: Pabis A 

PROVIDER: S-EPMC3970850 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature