title: Theoretical study of the hydroxylation of phenols mediated by an end-on bound superoxo-copper(II) complex.
abstract: Peptidylglycine alpha-amidating monooxygenase and dopamine beta-monooxygenase are copper-containing proteins which catalyze essential hydroxylation reactions in biological systems. There are several possible mechanisms for the reductive O(2)-activation at their mononuclear copper active site. Recently, Karlin and coworkers reported on the reactivity of a copper(II)-superoxo complex which is capable of inducing the hydroxylation of phenols with incorporated oxygen atoms derived from the Cu(II)-O(2) (.-) moiety. In the present work the reaction mechanism for the abovementioned superoxo complex with phenols is studied. The pathways found are analyzed with the aim of providing some insight into the nature of the chemical and biological copper-promoted oxidative processes with 1:1 Cu(I)/O(2)-derived species.
authors.affiliation: Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Gerona, Spain.
authors.forename: Mireia
authors.initials: M
authors.lastname: Güell
authors.forename: Josep M
authors.initials: JM
authors.lastname: Luis
authors.forename: Per E M
authors.initials: PE
authors.lastname: Siegbahn
authors.forename: Miquel
authors.initials: M
authors.lastname: Solà
mesh_terms: D002384:Catalysis; D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D006900:Hydroxylation; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry*; D013481:Superoxides / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D010636:Phenols; D013481:Superoxides; D003300:Copper