Camargo Tiago P, Maia Fernanda F, Chaves Cláudia, de Souza Bernardo, Bortoluzzi Adailton J, Castilho Nathalia, Bortolotto Tiago, Terenzi Hernán, Castellano Eduardo E, Haase Wolfgang, Tomkowicz Zbigniew, Peralta Rosely A, Neves Ademir
Departamento de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, SC, Brazil.
Centro de Biologia Molecular Estrutural, Departamento de Bioquímica, Universidade Federal de Santa Catarina, Florianópolis 88040-900, Brazil.
J Inorg Biochem. 2015 May;146:77-88. doi: 10.1016/j.jinorgbio.2015.02.017. Epub 2015 Mar 5.
Herein, we report the synthesis and characterization of the new di-iron(III) complex [(bbpmp)(H2O)(Cl)Fe(III)(μ-Ophenoxo)Fe(III)(H2O)Cl)]Cl (1), with the symmetrical ligand 2,6-bis{[(2-hydroxybenzyl)(pyridin-2-yl)methylamino]methyl}-4-methylphenol (H3bbpmp). Complexes 2 with the unsymmetrical ligand H2bpbpmp - {2-[[(2-hydroxybenzyl)(2-pyridylmethyl)]aminomethyl]-6-bis(pyridylmethyl) aminomethyl}-4-methylphenol and 3 with the ligand L(1)=4,11-dimethyl-1,8-bis{2-[N-(di-2-pyridylmethyl)amino]ethyl}cyclam were included for comparison purposes. Complex 1 was characterized through elemental analysis, X-ray crystallography, magnetochemistry, electronic spectroscopy, electrochemistry, mass spectrometry and potentiometric titration. The magnetic data show a very weak antiferromagnetic coupling between the two iron centers of the dinuclear complex 1 (J=-0.29cm(-1)). Due to the presence of labile coordination sites in both iron centers the hydrolysis of both the diester model substrate 2,4-BDNPP and DNA was studied in detail. Complex 1 was also able to catalyze the oxidation of the substrate 3,5-di-tert-butylcatechol (3,5-DTBC) to give the corresponding quinone, and thus it can be considered as a catalytically promiscuous system.
在此，我们报道了新型二价铁（III）配合物[(bbpmp)(H₂O)(Cl)Fe(III)(μ - 苯氧基)Fe(III)(H₂O)Cl]Cl（1）的合成与表征，其配体为对称的2,6 - 双{[(2 - 羟基苄基)(吡啶 - 2 - 基)甲基氨基]甲基}-4 - 甲基苯酚（H₃bbpmp）。为作比较，还纳入了具有不对称配体H₂bpbpmp - {2 - [[(2 - 羟基苄基)(2 - 吡啶基甲基)]氨基甲基]-6 - 双(吡啶基甲基)氨基甲基}-4 - 甲基苯酚的配合物2以及具有配体L(1)=4,11 - 二甲基 - 1,8 - 双{2 - [N - (二 - 2 - 吡啶基甲基)氨基]乙基}环胺的配合物3。配合物1通过元素分析、X射线晶体学、磁化学、电子光谱、电化学、质谱和电位滴定进行表征。磁性数据表明双核配合物1的两个铁中心之间存在非常弱的反铁磁耦合（J = - 0.29cm⁻¹）。由于两个铁中心均存在不稳定的配位位点，因此对二酯模型底物2,4 - BDNPP和DNA的水解进行了详细研究。配合物1还能够催化底物3,5 - 二叔丁基邻苯二酚（3,5 - DTBC）氧化生成相应的醌，因此可被视为一种催化混杂体系。
