柔性四吡啶配体的钴(Ⅱ)配合物的合成及其结构和性质  

Synthesis,structure and properties of cobalt(Ⅱ) complex with a flexible tetrapyridyl ligand

作　　者：陈飞 吴敏 李其军 黄玉珍 邓学良 黄利 江李波 张华新 CHEN Fei;WU Min;LI Qi-jun;HUANG Yu-zhen;DENG Xue-liang;HUANG Li;JIANG Li-bo;ZHANG Hua-xin(College of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China;Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development,Nanning 530004,China)

机构地区：[1]广西大学化学化工学院,广西南宁530004 [2]广西高校应用化学技术与资源开发重点实验室,广西南宁530004

出　　处：《广西大学学报（自然科学版）》2018年第5期2034-2040,共7页Journal of Guangxi University（Natural Science Edition）

基　　金：国家自然科学基金资助项目(21561003);广西自然科学基金资助项目(2015GXNSFCB139003);广西大学科研启动基金资助项目(XDZ140116);"大学生创新创业训练计划"资助项目(201810593039)

摘　　要：贵金属水氧化催化剂因价格昂贵而致其实际应用受限制,因此迫切需要开发非贵金属催化剂。为了寻找成本低廉、容易合成且具有理想的氧化还原电位等优势、水溶性良好的钴配合物催化剂,文中报道了柔性多吡啶基配体tpbn(N,N,N',N'-四(2-吡啶甲基)-1,4-丁二胺)的钴(Ⅱ)配合物[Co(tpbn)](ClO_4)_2(1)的合成及其结构和性质。X-射线单晶衍射分析表明,配合物(1)是单核配合物。在分子结构中,钴离子处于一个八面体配位环境中,每个钴中心金属离子的六个配位点全部被同一个tpbn的四个吡啶基上的氮和两个氨基上的氮所占据,两个高氯酸根作为抗衡离子存在。在0. 1 mol/L的磷酸缓冲溶液中,循环伏安图显示在0. 30 V出现一对氧化还原峰,归属为配合物的氧化还原过程CoⅢ/Ⅱ。紫外可见光谱测定表明,在500 nm左右有吸收峰,归属为d-d跃迁。Since the practical application of the water oxidation catalysts based on noble metals is greatly limited,it is urgent to develop non-noble metal based molecular catalysts.Among them,cobalt complexes are low cost,easily synthesized and show ideal redox properties.Therefore,the development of cobalt complex-based catalysts with good water solubility has become one of the focuses of current research.Herein reported is the synthesis,structure and properties of complex[Co(tpbn)](ClO 4)2(1)with the flexible tetrapyridyl ligand N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine(tpbn).X-ray single crystallography analysis reveals that complex(1)is a mononuclear complex.The cobalt(II)ion is located in an octahedron environment which is composed of six nitrogen atoms from the four pyridyl and two amino groups of a tpbn.Two perchlorate ions serve as counteranions.The cyclic voltammogram of complex(1)in 0.1 mol/L phosphate buffer solutions shows a redox wave at 0.30 V,which is assigned to the process of CoⅢ/Ⅱ.The UV-visible spectrum of complex(1)displays one band centered at about 500 nm,attributed to the d-d transition.

关 键 词：钴配合物 晶体结构 氧化还原 

分 类 号：O614.812[理学—无机化学]