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 HClO4. The β-pyrrole nitro-substituted derivatives were shown to be better catalysts than the non-nitro substituted compounds under the utilized experimental conditions.

Two free-base and four metal derivatives of substituted tetraarylporphyrins containing a nitro-substituent on the β-pyrrole position of the macrocycle were synthesized and characterized by UV-vis, FTIR, 1 H NMR and mass spectrometry as well as electrochemistry and spectroelectrochemistry in non-aqueous media. The porphyrins are represented as ( NO 2 TmPP ) M and ( NO 2 TdmPP ) M , where M = 2 H , Fe III Cl or Mn III Cl , m is a CH 3 group on the para-position of the four meso-phenyl rings of the tetraphenylporphyrin (TPP) and dm represents two OCH 3 substituents on the meta-positions of each phenyl ring of the TPP macrocycle. UV-visible spectra of the nitro-substituted porphyrins exhibit absorption bands which are red-shifted by 4–11 nm as compared to bands of the same substituted tetraarylporphyrins lacking a nitro substituent. Three or four reductions are observed for each iron and manganese nitroporphyrin, the first of which is metal-centered, leading to formation of an Fe ( II ) or Mn ( II ) complex. Further reduction at the metal center occurs for the iron porphyrins but this reaction proceeds via an Fe ( II ) π anion radical in the case of the two nitro-substituented derivatives. The β-nitro-substituted porphyrins are easier to reduce and harder to oxidize than the corresponding compounds lacking a nitro group. The effect of NO 2 substituent on reduction/oxidation potentials and the site of electron transfer was also discussed.