Covalent Linkage of the Type-2 and Type-3 Structural Mimics to Model the Active Site Structure of Multicopper Oxidases: Synthesis and Magneto- Structural Properties of Two Angular Trinuclear Copper(II) Complexes
作者:Arindam Mukherjee、Indranil Rudra、Sunil G. Naik、Suryanarayanasastry Ramasesha、Munirathinam Nethaji、Akhil R. Chakravarty
DOI:10.1021/ic034565i
日期:2003.9.1
of a trinuclear copper(II) unit formed by the covalent linkage of monomeric type-2 mimic and dimeric type-3 mimic precursor complexes to give an angular arrangement of the metal atoms in the core which is a model for the active site structure of blue multicopper oxidases. In 1 and 2, the coordination geometry of two terminal copper atoms is distorted square-planar. The central copper has a distorted
两种新的配方为[Cu(3)(HL)LL'](ClO(4))的三角三核铜(II)络合物,其中L'为咪唑(Him,1)或1-甲基咪唑(1-MeIm,2) H [3] L是由水杨醛与1,3-二氨基丙烷-2-醇(摩尔比为2:1)缩合得到的席夫碱,是由[Cu(2)L(mu-Br) ]和[Cu(HL)]在L'存在下分离为高氯酸盐。1和2的晶体结构由三核铜(II)单元组成,该三核铜(II)单元是通过单体2型模拟物和二聚体3型模拟物前体复合物的共价键合形成的,从而在芯中给出金属原子的角排列,即蓝色多铜氧化酶活性位点结构的模型。在图1和图2中,两个末端铜原子的配位几何形状扭曲成方形。中心铜具有扭曲的方金字塔形(4 + 1)几何形状。Cu ... Cu的平均距离约为3.3A。该配合物具有双酚氧基桥联的dicopper(II)单元,该酚氧基氧原子呈平面几何形状。另外,该配合物具有内源的烷氧基桥联的双铜(II)单
Colored species formation between mononuclear copper(II) complex and superoxide anion
N,N′-(2-Hydroxy-propane-1,3-diyl)bis(salicylaldiminato)copper(II) was found to be an effective catalyst for the oxidation of ethanol, n-propanol, or hydroxyacetone in the presence of KOH under O2; the X-ray crystal structure shows that the co-ordination geometry of the copper is significantly distorted toward tetrahedral from square planar with two oxygens and two nitrogens from salicyladimine moieties