Synthesis and electrochemistry of β-pyrrole nitro-substituted cobalt(ii) porphyrins. The effect of the NO2 group on redox potentials, the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media

Abstract

Four cobalt(II) porphyrins, two of which contain a β-pyrrole nitro substituent, were synthesized and characterized by electrochemistry and spectroelectrochemistry. The investigated compounds are represented as (TRPP)Co and (NO₂TRPP)Co, where TRPP is the dianion of a substituted tetraphenylporphyrin and R is a CH₃ or OCH₃ substituent on the four phenyl rings of the macrocycle. Two reductions and three oxidations are observed for each compound in CH₂Cl₂ containing 0.10 M tetra-n-butylammonium perchlorate. The first reduction of the compounds without a nitro substituent is metal-centered and leads to formation of a Co(I) porphyrin which then reacts with the CH₂Cl₂ solvent to generate a carbon σ-bonded Co^III–R complex. A further reduction then occurs at more negative potentials to generate an unstable Co(II) σ-bonded compound. In contrast to these reactions, the first reduction of the nitro-substituted porphyrins is macrocycle-centered under the same solution conditions and gives a Co(II) porphyrin π-anion radical product. This reversible electron transfer is then followed at more negative potentials by a second reversible one-electron addition to give a Co(II) dianion. Three reversible one-electron oxidations are also seen for each compound. The first is metal-centered and the next two involve the conjugated π-system of the macrocycle. Each neutral Co(II) porphyrin was also examined as to its catalytic activity for electroreduction of molecular oxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO_4. The β-pyrrole nitro-substituted derivatives were shown to be better catalysts than the non-nitro substituted compounds under the utilized experimental conditions.