title: Theoretical investigations on the reaction of monosubstituted tertiary-benzylamine selenols with hydrogen peroxide.
abstract: The effects of introducing electron-donating (NH(2), OCH(3), CH(3)) and electron-withdrawing (NO(2), CF(3), CN, F) groups to N,N-dimethylbenzylamine-2-selenol are studied to determine the effect of the selenium electron density on the efficiency of the reduction of hydrogen peroxide. Introducing substituents in the meta and para positions decreases or increases the energy barrier of the reaction in the expected way, due to changes in the electronic environment of the reacting selenium center. Ortho substituents are found to have a greater effect on the electronic environment of the selenium center, which is mitigated by changing the steric environment. Insight into the origins of the substituent effects is obtained through quantum theory of atoms in molecules (QTAIM) and electrostatic potential analysis.
authors.affiliation: Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3.
authors.forename: Gavin S
authors.initials: GS
authors.lastname: Heverly-Coulson
authors.forename: Russell J
authors.initials: RJ
authors.lastname: Boyd
mesh_terms: D006861:Hydrogen Peroxide / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D016566:Organoselenium Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: C554905:N,N-dimethylbenzylamine-2-selenol; D016566:Organoselenium Compounds; D006861:Hydrogen Peroxide