title: A dicopper complex with distant metal centers. Structure, magnetic properties, electrochemistry and catecholase activity.
abstract: The crystal structure and magnetic properties of a dinuclear copper(II) complex of the ligand [2,8-dimethyl-5,11-di-(dimethylethyleneamine) 1,4,5,6,7,10,11,12-octahydroimidazo [4,5-h] imidazo [4,5-c] [1,6]diazecine] dimeim have been investigated. Also, its catecholase activity has been explored in different solvent mixtures: MeCN/H2O and OH/H2O, each at several pH values. In CH3OH/H2O, where the activity was superior, the optimal pH value for the catalytic activity was found to be lower than in CH3CN/H2O. The study of the complex's electrochemical behavior (cyclic voltammetry) which was also investigated in these various media, revealed that although an increase in pH in both solvent mixtures results in an increase both in Me oxidizing power (E(1/2)) and reversibility (ipa/ipc) the change of solvent system seems to be a more influencing factor. The superior catalytic activity found in MeOH/H2O pH=8.0, is associated with a significantly more reversible behavior displayed in this medium. Potentiometric determination of the overall formation constant and three successive pKas for the complex, suggest the formation of stable hydroxo complexes which could be the catalytically active species.
authors.affiliation: Universidad Nacional Autónoma de México, Facultad de Química, Departamento de Química Inorgánica, Cd. Universitaria, 04510 México DF, Mexico. gasquel@servidor.unam.mx
authors.forename: Laura
authors.initials: L
authors.lastname: Gasque
authors.forename: Víctor Manuel
authors.initials: VM
authors.lastname: Ugalde-Saldívar
authors.forename: Ingrid
authors.initials: I
authors.lastname: Membrillo
authors.forename: Juan
authors.initials: J
authors.lastname: Olguín
authors.forename: Edgar
authors.initials: E
authors.lastname: Mijangos
authors.forename: Sylvain
authors.initials: S
authors.lastname: Bernès
authors.forename: Ignacio
authors.initials: I
authors.lastname: González
mesh_terms: D016227:Benzoquinones / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D006575:Heterocyclic Compounds, 3-Ring / Q000737:chemistry*
chemical_list: D016227:Benzoquinones; D006575:Heterocyclic Compounds, 3-Ring; C530403:dimeim; C054466:3,5-di-tert-butyl-1,2-benzoquinone; D003300:Copper