Electrooxidation of porphyrin free bases: Fate of the π-cation radical

Inisan, C.
Saillard, J.-Y.
Guilard, R.
Tabard, A.
Le Mest, Y.

Publication date

January 1998

Publisher

Royal Society of Chemistry (RSC)

Abstract

International audienceIn contrast to metalloporphyrins with non-electroactive metal centres, the π-cation radicals of porphyrin free bases (H2OEP, H2TPP, H2CdiE) electrogenerated in strictly anhydrous solvents are not stable and give rise to a quantitative chemical reaction. Conjunction of electrochemical and spectroscopic data (UV/VIS, EPR and NMR) demonstrates unambiguously that the porphyrin skeleton is not modified during the chemical reaction. The reaction product is the protonated free base, and thus the free base can be regenerated by reduction of the protons