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Citation: Yan Chuanwei, Liu Yayan, Li Jie, Lin Xiangqin. Mechanism Study on Electrochemical Reduction of Co(Ⅱ)TPP/Cyclohexyl Bromide System[J]. Chinese Journal of Applied Chemistry, ;1995, 12(6): 33-37. shu

Mechanism Study on Electrochemical Reduction of Co(Ⅱ)TPP/Cyclohexyl Bromide System

Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun 130022

Received Date: 9 February 1995
Revised Date: 25 June 1995

The mechanism of electrochemical reactions of electrogenerated Co(Ⅰ) TPP and cyclohexyl bromide was investigated with cyclic voltammetry,in-situ ESR-spectroelec-trpchemistry and in-situ micro-electrode-CV thin-layer electrochemistry in DMF solution. The redox reaction of Co(Ⅱ) /Co(Ⅰ) parallelly catalyzed the reduction of cyclohexyl bromide,and generated both the cyclohexyl radicals and Co-C bond compound C₆H₁₁Co(Ⅲ)TPP. Further reduction of the Co-C bond compound at-1.30V(SCE) im-plied an EC mechanism,namely electrochemical reduction followed by Co-C bond splitting reaction which regenerated the cyclohexyl radicals with rate constant of 0.73s^-1. The pres-ence of additional CH₂=CHCN led to the generation of a new Co-C bond compound which gave rise to a reduction peak at -1.10V(SCE). A mechanism for the Co(Ⅱ) TPP/cyclo-hexyl bromide system, suggesting that the cyclohexyl bromide primarily reacts with electro-generated Co(Ⅰ) TPP via the production of the cyclohexyl radicals,has been proposed.
- cobalt tetraphenylporphyrn,
- electrochemical redox reaction,
- cyclohexyl bromide,
- in-situ ESR
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