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.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.