四种钌(Ⅱ)配合物的中心离子电化学行为的比较  

Comparative Study of the Electrochemical Behavior of the Central lons of Four Ruthenium (Ⅱ) Complexes

作　　者：李红[1] 巢晖[1] 蒋雄[2] 计亮年[1] 

机构地区：[1]中山大学化学与化学工程学院,广州510275 [2]华南师范大学化学系,广州510631

出　　处：《物理化学学报》2001年第8期728-732,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(29871036);广东省自然科学基金(970211;990452)资助项目

摘　　要：应用循环伏安、循环交流伏安和微分电容技术等电化学方法研究了由 Ｒｕ（Ⅱ）与 ２，２’－联吡啶（ｂｐｙ）、１，１０－邻菲咯啉（ｐｈｅｎ）和桥联配体１，４－二［２－咪唑并［４，５－ｆ］邻菲咯啉］苯（ＤＩＰＢ）配位而成的四种配合物［Ｒｕｌ：Ｒｕ（ｂｐｙ）２ＤＩＰＢ（ＣｌＯ４）２、ＲＵ２：（ｂｐｙ）２Ｒｕ（ＤＩＰＢ）Ｒｕ（ｂｐｙ）２（ＣｌＯ４）４、Ｒｕ３：Ｒｕ（ｐｈｅｎ）２ＤＩＰＢ（ＣｌＯ４）２和 Ｒｕ４：（ｐｈｅｎ）２ ＲＵ（ＤＩＰＢ）Ｒｕ（ｐｈｅｎ）２（ＣｌＯ４）４］在铂电极上的电化学行为及金属间的相互作用. 研究结果表明，在高氯酸四丁基铵（ＴＢＡＰ）的乙腈溶液中，单、双核中心离子在循环伏安图上分别呈现１对可逆的１电子和２电子的氧化还原波，单核对应的配位阳离子的扩散系数较双核的大，辅助配体为ｂｐｙ的配位阳离子的扩散系数较ｐｈｅｎ的大应用循环交流伏安法和微分电容技术研究则发现，双核中心离子的氧化还原过程表现为２个连续单电子过程的重叠。The electrochemical behavior of mononuclear and symmetrical binuclear ruthenium(Ⅱ) complexes [Rul: Ru (bpy)2DIPB (ClO4 )2, Ru2: (bpy )2 Ru (DIPB )Ru (bpy )2 (ClO4)4, Ru3: Ru (phen)2DIPB (ClO4)2 and Ru4: (phen)2 Ru(DIPB )Ru (phen)2 (ClO4)4] containing binuclear ligand 2, 2'-bipyridine(bpy), 1, 10-phenanthroline (phen ) and bridging ligand 1, 4-di- [2-imidazo [4, 5-f] [1, 10] phenanthroine benzene (DIPB ) on a platinum electrode and the intermetallic interaction of binuclear complexes have been investigated using cyclic voltammetry, cyclic ac voltammetry and differential capacitance techniques, etc. In acetonitrile solution with a concentration of 0. 1 mol· dm -3 TBAP, the central ions in four complexes all display single le and 2e reversible oxidation- reduction waves on the cyclic voltammograms, with apparent diffusion coefficients of the mononuclear complexed cations being larger than that of the binuclear ones. The apparent diffusion coefficients for complexed cations with auxiliary ligands bpy are also found to be larger than that with ligands phen. It appears that the overlapping of two continuous sin- gle-electron processes by cyclic ac voltammetry and differential capacitance techniques occurs during the redox processes of the central ions binuclear complexes. The results show that a weak electronic interaction exits between the two central ruthenium ions in binuclear complexes.

关 键 词：铒(Ⅱ)配合物 铂电极 中心离子 电化学行为 循环伏安法 交流伏安法 

分 类 号：O641.4[理学—物理化学]