中性配体存在下(OEP)Co的电化学和光谱电化学研究  

Electrochemical and Spectroelectrochemical Study of (OEP)Co in the Presence of Acrylonitrile, Ethanol, N,N-dimethylformamide and Dimethylsulfoxide in Dichloroethane Solution

作　　者：林祥钦[1] 严川伟[2] 

机构地区：[1]中国科学院长春应用化学研究所电分析化学实验室 [2]国家电化学和光谱研究分析中心,长春130022

出　　处：《化学学报》1997年第6期521-526,共6页Acta Chimica Sinica

基　　金：国家自然科学基金资助的课题

摘　　要：本文以循环伏安跟踪的电化学滴定,结合现场紫外-可见薄层光谱电化学方法,研究了丙烯膊、乙醇、二甲基甲酸胺和二甲基亚砜等电中性轴向配体的配位反应及其对(OEP)Co三步单电子氧化步骤的影响,计算了(OEP)Co(Ⅲ)与四种配体的配合常数,表明配位能力的大小顺序为丙烯腈<乙醇<二甲基甲酸胺<二甲基亚砜(OEP)Co(Ⅲ)可以和一个或两个丙烯腈或乙醇分子形成五配位或六配位的化合物,但是只出现和两个二甲基甲酰胺或二甲基亚砜分子形成六配位化合物;发现(OFP)Co(Ⅱ)并不与这些配体在轴向配位.在环阳离子自由基状态下,钴中心的配位性依然存在但强度减小.讨论了这些体系的电化学-配位反应机理.The ligand effects of acrylonitrile, EtOH, DMF and DMSO on the electrochemical oxidation reactions of (OEP)Co were investigated by CV monitored electrochemical titration and in - situ thin- layer spectroelectrochemical method. The formation constants of (OEP)Co(III) with these molecules were calculated. The magnitude of the values shows the order of acrylonitrile <EtOH<DMF<DMSO. It was demonstrated that the Co(III) center can coordinate with one or two of these molecules. However, the Co(II) center does not show any coordination with any of these molecules. It was also find that the ring cation radicals of the Co(III) can form one or two axial bindings with these molecules.

关 键 词：八乙基钴卟啉 电化学滴定 光谱电化学 钴卟啉 

分 类 号：O614.812[理学—无机化学]