A new dinuclewr unsymmetric copper(II) complex as model for the active site of catechol oxidase

摘要

The crytal structure, magnetic, redox and spectroscopic properties of a novel unsymmetrical dinuclear copper(II) complex, prepared by the reaction between copper(II) perchlorate, sodium acetate and the unsymmetrical, binucleating ligand HTPPNOL, where HTPPNOL is N,N,N'-tris-(2-pyridylmethyl)-1,3-diaminopropan-2-ol, is reported. HTPPNOL (l equiv.) reacted with l equiv. of coper(II) ion, in methanol, and produced the mononuclear copper complex [Cu(TPPNOL)](ClO_4)(BBh_4) (1). On the other hand, the reaction of l equiv. of HTPPNOL with 2 equiv. each of copper (II) ion and acetate, in methanol, produced the dinuclear complex [Cu_2(TPPNOL)(OOCCH_3)](ClO_4)_2 (2), whose structrue has been determined by X-ray diffraction. In complex 2, as a result of the inherent asymmetry of the ligand HTPPNOL, one copper ion is five-coordinated (distorted trigonal-bipyra-midal) while the other copper is four-coordinated (distorted square-planar). Then, as a result of the presence of distinct geometries for the metal centres, complex 2 exhibits a ferromagnetic coupling (J = + 25.41 cm~(-1)). Titrationn experiments carried out on the dinuclear complex suggest a pK_a = 8.0, which was related to the aquo/hydroxo equilibrium. Complex 2 is able to oxidise 3,5-di-tert-butylcatechol to the respective o-quinone. The oxidation was studied by following the appearance of the quinone spectrophotometrically, at pH 8.0 and 25 deg C.