Low Temperature Studies of Electrochemical Kinetics I . Cyclic Voltammetry of Diethyl Fumarate
Low Temperature Studies of Electrochemical Kinetics I . Cyclic Voltammetry of Diethyl Fumarate
复制标题
电化学动力学的低温研究I．
DOI：
10.1149/1.2134218
复制
发表时间：
1975
影响因子：
3.9
通讯作者：
J. T. Maloy
中科院分区：
文献类型：
--
作者：
R. Grypa;J. T. Maloy
对富马酸二乙酯（DEF）在二甲基甲酰胺（DMF）中进行了描述性、低温、循环伏安法研究。温度变化低至200℃，揭示了三个相互关联的还原过程。第一个和第二个对应DEF和DEF=；第三种是归因于初始还原的二聚体产物的还原。温度降低抑制了这种二聚体产物的形成，同时提高了DEF-还原为DEF=的可用性。在降低温度下，DEF=的广泛形成似乎伴随着电极表面的薄膜。这表明聚合可能通过DEF=进行，实际上可能被二聚化过程所抑制。水的加入增强了第三还原峰；它还减少了可用的阴极电位范围，使该峰值在室温下的背景中消失。温度降低增加了有效电位范围，从而可以研究水加速电加氢二聚反应的产物。1,2 -二活烯烃的电加氢二聚反应已被许多研究者研究。这些EHD反应具有重要的合成意义，因为它们通常被认为是形成“活的”聚合物的第一步。最近的研究（2-4）也表明，这些反应也可用于电引发某些环化。
Descriptive, low temperature, cyclic voltammetry studies have been conducted upon diethyl fumarate (DEF) in dimethylformamide (DMF). Temperature variations down to 200~ reveal three, interrelated, reduction proceSses. The first and second correspond to the formation of DEF and DEF=; the third is attributed to the reduction of a dimeric product of the initial reduction. Temperature reduction inhibits the formation of this dimeric product while enhancing the availability of DEF-for reduction to DEF= The extensive formation of DEF= at reduced temperatures appears to be accompanied by a filming of the electrode surface. This suggests that polymerization may proceed through DEF= and may actually be inhibited by the dimerization process. The addition of water enhances the third reduction peak; it also decreases the available cathodic potential range so that this peak becomes lost in background at room temperature. Temperature reduction increases the available potential range so that products of the water-accelerated electrohydrodimerization reaction may be studied.The electrohydrodimerization (EHD) reactions of 1, 2-diactivated olefins have been studied by many investigators. These EHD reactions are of synthetic interest because they are generally regarded as the first step in the formation of the" living" polymer (1). Recent studies (2-4) have also indicated that these reactions may also be used to electroinitiate certain cyclizations.