摘要
在醋酸-醋酸钠缓冲溶液中,使用[α-A-GeW_9O_(34)]^(10-)代替[α-A-PW_9O_(34)]^(9-)配体,成功合成了新型结构的Ce(Ⅳ)夹心型配合物((NH_4)Na_2H_7[Ce_4O_2(CH_3COO)_2(α-AGeW_9O_(34))_2]·17H_2O),通过元素分析、X射线单晶衍射、IR、TG、NMR和XPS等表征技术确定了配合物组成和结构,研究了配合物的电化学性质.在配合物中Ce(Ⅳ)有2种配位模式,每个Ce(1)与2个缺位多酸的6个氧、2个三桥氧配位连接,每个Ce(2)与2个缺位多酸的5个氧、1个三桥氧和醋酸根中的2个氧配位连接,分别形成八配位四方反棱柱结构.通过对配合物的电化学分析发现,与硝酸铈铵相比,配合物中Ce(Ⅳ/Ⅲ)的阳极峰电势由0.906V减小至0.877V,证明多酸阴离子配体有稳定Ce(Ⅳ)的作用.
By employing [α-A-GeW_9O_（34）]^（10-）instead of [α-A-PW_9O_（34）]^（9-）,we have synthesized a Ce（Ⅳ）sandwich complex with a novel structure in the sodium acetate buffer solution（pH = 5.0）.（（NH_4）Na_2H_7[Ce_4O_2（CH_3COO）_2（α-A-GeW_9O_（34））_2]·17H_2O）.By empolying elmental analysis,Xray single crystal diffraction,IR,TG,13 C NMR and XPS,the composition and structure have been invetigated and the electrochemistry has been studied.There are two coordination models：each Ce（1）is coordinated with two oxygen atoms of two[α-A-GeW_9O_（34）]^（10-）ligands,twoμ3-bridged oxygen atoms and each Ce（2）is coordinated with five oxygen atoms of two[α-A-GeW_9O_（34）]^（10-）ligands,oneμ3-bridged oxygen atoms and two oxygen atoms of a acetate ion,forming 8-coordinated square antiprism geometry.Electrochemical analysis of complex indicate that,compared with ammonium ceric nitrate,tetravalent cerium ion anodic peak negative shift to 0.877 V,indicating that Ce（Ⅳ）ions can be stabilized by[α-A-GeW_9O_（34）]^（10-）ligand.
出处
《辽宁师范大学学报（自然科学版）》
CAS
2016年第3期377-384,共8页
Journal of Liaoning Normal University:Natural Science Edition
基金
国家自然科学基金资助项目(21573099)
