Gasque Laura, Ugalde-Saldívar Víctor Manuel, Membrillo Ingrid, Olguín Juan, Mijangos Edgar, Bernès Sylvain, González Ignacio
Universidad Nacional Autónoma de México, Facultad de Química, Departamento de Química Inorgánica, Cd. Universitaria, 04510 México DF, Mexico.
J Inorg Biochem. 2008 May-Jun;102(5-6):1227-35. doi: 10.1016/j.jinorgbio.2007.12.032. Epub 2008 Jan 11.
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.
对配体[2,8 - 二甲基 - 5,11 - 二 -(二甲基乙二胺)1,4,5,6,7,10,11,12 - 八氢咪唑并[4,5 - h]咪唑并[4,5 - c][1,6]二氮杂环辛四烯]二亚胺的双核铜(II)配合物的晶体结构和磁性进行了研究。此外,还在不同的溶剂混合物中探索了其邻苯二酚酶活性:乙腈/水和甲醇/水,每种在几个pH值下。在活性较高的甲醇/水中,发现催化活性的最佳pH值低于乙腈/水。在这些不同介质中也对该配合物的电化学行为(循环伏安法)进行了研究,结果表明,虽然两种溶剂混合物中pH的增加都会导致氧化能力(E(1/2))和可逆性(ipa/ipc)的增加,但溶剂体系的变化似乎是一个更具影响的因素。在甲醇/水pH = 8.0时发现的较高催化活性与该介质中显著更可逆的行为有关。对该配合物的总形成常数和三个连续pKa的电位滴定测定表明形成了稳定的羟基配合物,这些配合物可能是催化活性物种。