草酰胺桥联大环二羰四胺铜(Ⅱ)-钴(Ⅱ)异双核配合物的合成、结构、表征和电化学性质  

Synthesis、Structure Characterization and Electrochemical Property of Cu(Ⅱ)-Co(Ⅱ) Heterobinuclear Complex from an Oxalamide Bridged Macrocyclic Dioxotetraamines

作　　者：陶偌偈[1] 臧双全[1] 赵阁[1] 娄本勇[1] 牛景扬[1] 周绪亚[1] 

机构地区：[1]河南大学化学化工学院,开封475001

出　　处：《应用化学》2002年第5期459-463,共5页Chinese Journal of Applied Chemistry

基　　金：河南省杰出青年基金和河南省自然科学基金资助项目

摘　　要：合成了一种具有草酰胺桥联大环二羰四胺结构的 Cu( ) -Co( )异双核配合物 ,用红外光谱、电子光谱、摩尔电导、热重分析、室温磁矩、循环伏安等对其进行了表征 .初步推定 Cu( ) -Co( )异双核配合物具有草酰胺桥联大环二羰四胺结构 .室温磁矩测定表明 ,通过草酰胺桥联配体金属离子间有一定的反铁磁性自旋偶合作用 .循环伏安法测定了配合物的半波电位 ,实验表明 ,此类配合物能够稳定高价态 Cu( ) ,外延桥基配位对大环内腔 Cu( )离子的氧化还原过程无影响 .单核配合物 X射线晶体衍射研究表明 ,其为单斜晶系 ,空间群 P2 1 /c,a=0 .73 861 (1 5 ) nm,b=2 .1 2 1 1 (4 ) nm,c=0 .95 2 5 0 (1 9) nm,β=94.70 (3 )°,R1 =0 .0 5 1 3 ,w R2 =0 .1 1 77,Z=4.Cu( )处于大环四胺平面正方中心上方 0 .0 3 nm。Cu(Ⅱ) Co(Ⅱ) heterobinuclear complex was synthesized from an oxalamide bridged macrocyclic dioxotetraamines and characterized by IR, UV visible spectra, molar conductivity, thermogravity analysis, cyclic voltammetry and room temperature magetic moment measurements. The results suggested the Cu(Ⅱ) Co(Ⅱ) heterobinuclear complex has an oxalamide brideged structure with copper(Ⅱ) being in a planar and cobalt(Ⅱ) in an octahedral environment. Room temperature magetic studies showed that there are weak antiferromagetic interactions between the two metal ions within a molecule. Cyclic voltammetry studies showed this complex can stabilize higher oxidation states of Cu(Ⅲ) . Mononuclear Cu(Ⅱ) complex is of monoclinic system, space group P2 1/c , a = 0 7386 1(15) nm , b=2 121 1(4) nm, c =0 952 50(19) nm, β =94 70(3)° and Z =4. Fall matrix least squares refinement of the structure led to a conventional weighted R factor of 0 051 3 .

关 键 词：晶体结构 异双核配合物 循环伏安 

分 类 号：O614[理学—无机化学]