Mechanistic insight on the catecholase activity of dinuclear copper complexes with distant metal centers
Por:
Mendoza-Quijano M.R., Ferrer-Sueta G., Flores-Álamo M., Aliaga-Alcalde N., Gómez-Vidales V., Ugalde-Saldívar V.M., Gasque L.
Publicada:
1 ene 2012
Categoría:
Inorganic Chemistry
Resumen:
The catecholase activity of two dinuclear Cu(II) complexes with distant metal centers is discussed together with solid state and solution studies. The crystal structure for one of them, [Cu-2(diep)(H2O)(4)] (ClO4)(4)center dot 2H(2)O, is described, showing the two copper ions are 7.457 angstrom apart and in a square pyramidal coordination. Both complexes display a weak antiferromagnetic coupling in the solid state that is manifest in the dimer EPR spectra obtained in frozen solution. The pH-potentiometric speciation performed in 1 : 1 MeOH H2O allowed the assignment of hydrolyzed copper species as those catalytically active in the oxidation of 3,5-di-tert-butylcatechol (DTBC). The kinetic measurements led us to propose behavior consistent with Michaelis-Menten plus a linear dependence of the initial rate on [DTBC]. This can be associated with the presence of more than one catalytically active species, which is consistent with the evidence of several differently hydrolyzed species shown
Filiaciones:
Mendoza-Quijano M.R.:
Univ Nacl Autonoma Mexico, Dept Quim Inorgan & Nucl, Fac Quim, Mexico City 04510, DF, Mexico
Ferrer-Sueta G.:
Laboratorio de Fisicoquímica Biológica, Facultad de Ciencias, Universidad de la República Iguá, 4225 11400 Montevideo, Uruguay
Flores-Álamo M.:
Univ Nacl Autonoma Mexico, Dept Quim Inorgan & Nucl, Fac Quim, Mexico City 04510, DF, Mexico
Aliaga-Alcalde N.:
ICREA-Departament de Química Inorgànica, Universitat de Barcelona Diagonal, 645 08028 Barcelona, Spain
Gómez-Vidales V.:
Univ Nacl Autonoma Mexico, Inst Quim, Mexico City 04510, DF, Mexico
Ugalde-Saldívar V.M.:
Univ Nacl Autonoma Mexico, Dept Quim Inorgan & Nucl, Fac Quim, Mexico City 04510, DF, Mexico
Gasque L.:
Univ Nacl Autonoma Mexico, Dept Quim Inorgan & Nucl, Fac Quim, Mexico City 04510, DF, Mexico
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