具有两种不同配位隔室的含酚桥基‘N_5O_2’Schiff碱大环铜钠异双核配合物的合成及结构  

Synthesis and Structure of Cu(II) and Na(I) Heterodinuclear Complex of Phenol-bridged‘N_5O_2' Schiff Base Ligand with Two Different Coordination Compartments

作　　者：马长勤[1] 张文兴[1] 王绪宁[1] 蒋德华[1] 

机构地区：[1]山东大学化学学院,济南250100

出　　处：《化学学报》1997年第6期539-544,共6页Acta Chimica Sinica

基　　金：山东大学青年科学基金资助课题

摘　　要：以Cu^(2+)和Na^+同时作为模板,用2,6-二甲酰基对甲苯酚直接与一定比例的乙二胺,二-1,2-亚乙基-三胺发生[2+2]型 Schiff碱缩合,合成了含两个不同隔室Schiff碱大环配体(L^2-)的铜钠异双核配合物[CuNaL(ClO_4)].并对它进行了元素分析,UV-Vis,IR,1H NMR,摩尔电导和ESR谱等项表征.ESR谱显示三个g值峰,对应的gx,gy,gz值分别为1.987,2.168,2.233.单晶X射线四圆衍射分析表明,该配合物为单斜晶系,空间群P2_1/n,晶胞参数a=0.9255(3)b=1.7689(2),c=1.6055(2)nm,β=101.69(2)°,Z=4,V=2.574nm.Cu原子和Na原子分别位于大环配体V^2-的‘N_2O_2’四配位和‘N_3O_2’五配位隔室.Cu^(2+)的配位数为4,基本保持平面构型、Cu—O和Cu—N平均键长分别为0.1911,0.1926nm,Na^+除与L^2-配位外,还与单齿高氯酸根结合,配位数为6.Na——O和Na——N的平均键长分别为0.2379,0.2468nm.Cu…Na间距离为0.3227nm.The title complex [CuNaL (ClO4) ] of a Robson macrocycle with two different coordination compartments H2L, derived from Schiff base condensation of 4 - methyl-2,6-diformylphenol and two kinds of diamine, has been synthesized in one template reaction. The complex has been characterized by UV - Vis, IR, 1H NMR and ESR spectra. The ESR spectrum shows three peaks at gx = 1. 987, gy = 2. 168 and gz=2. 233, respectively. The complex crystallizes in the monoclinic crystal system, space group P21/n , with Z = 4, a = 0.9255(3), b= 1.7689(2), c = 1.6055(2)nm,β= 101. 69(2)°,and V = 2.574(9)nm3. The refinementconverges with R =0.053 and Rw = 0.065 for 2640 reflections with I≥3σ(I). The Cu(II) and Na( I ) ions reside at the 4 - and 5 - coordination compartments of the macrocycle, respectively. The coordination geometry around the copper atom is regarded as a planar square. But the sodium atom is also coordinated with one oxygen atom of a perchlorate anion on the axis. This geometry of six - coordinate sodium may be considered as a pentagonal pyramid. The distance between Cu and Na bridged by two phenolic oxygens is 0.3227(3)nm.

关 键 词：铜 钠 异双核配合物 晶体结构 席夫碱 大环配体 

分 类 号：O625.632[理学—有机化学] O614.121[理学—化学]