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Published on: January 30, 2015
Substituent effects on the redox reactions of tetraphenylporphyrins
Abstract:
The effect of substituents on pi radical reactions of para-substituted tetraphenylporphyrins was investigated by cyclic voltammetry in methylene chloride. In all cases electron donating substituents produced a more difficult reduction and an easier oxidation. Plots of E1/2 vs. a yielded Hammett linear free energy relationships for cation radical and dication formation and anion radical and dianion formation. An average reaction constant of p=0.07+/-0.01 V was obtained. This was true for tetraphenylporphyrins containing the central metals VO, Mn, Fe, Co, Ni, Cu, and Zn, as well as the free base H2 (p-X)TPP. The value of p appears not to be directly affected by the central metal oxidation state or the overall charge on the complex.
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