title: Dehalogenation of aromatics by nucleophilic aromatic substitution.
abstract: Nucleophilic aromatic substitution has been implicated as a mechanism for both the biotic and abiotic hydrodehalogenation of aromatics. Two mechanisms for the aqueous dehalogenation of aromatics involving nucleophilic aromatic substitution with hydride as a nucleophile are investigated using a validated density functional and continuum solvation protocol. For chlorinated and brominated aromatics, nucleophilic addition ortho to carbon-halogen bonds via an anionic intermediate is predicted to be the preferred mechanism in the majority of cases, while concerted substitution is predicted to be preferred for most fluorinated aromatics. Nucleophilic aromatic substitution reactions with the hydroxide and hydrosulfide anions as nucleophiles are also investigated and compared.
authors.affiliation: Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich , 8092 Zurich, Switzerland.
authors.forename: Daniel
authors.initials: D
authors.lastname: Sadowsky
authors.forename: Kristopher
authors.initials: K
authors.lastname: McNeill
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
mesh_terms: D000838:Anions / Q000737:chemistry; D001554:Benzene / Q000737:chemistry; D004777:Environment; D054879:Halogenation; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D055601:Organic Chemistry Phenomena; D012996:Solutions; D013816:Thermodynamics
chemical_list: D000838:Anions; D006841:Hydrocarbons, Aromatic; D012996:Solutions; D001554:Benzene