Reductive nitrosylation of water-soluble iron porphyrins by S-nitroso-N-acetylpenicillamine: Rate constants and EPR characterization

Abstract

Reductive nitrosylation of the water-soluble iron derivatives of the cationic FeIII(TMPyP) and anionic FeIII(TPPS) porphyrins [where TMPyP=tetra-meso-(4-N-methylpyridiniumyl)porphinate and TPPS=tetra-meso-(4-sulfonatophenyl)porphinate] by the nitric oxide donor S-nitroso-N-acetylpenicillamine (SNAP) was studied using optical absorption spectroscopy and electron paramagnetic resonance. Nitrosylation rates were obtained, the reaction was found to be first order in the SNAP concentration and the stoichiometry of the reaction was one to one. The similarity between the obtained second-order rate constants for both porphyrins, kTMPyP=0.84×103M−1s−1 and kTPPS=0.97×103M−1s−1, suggested that the reaction mechanism is approximately independent of the nature of the porphyrin meso-substituents. A mechanism was proposed involving the hydrolysis of SNAP by an out of plane liganded H2O yielding the sulfenic acid of N-acetylpenicillamine and the transfer of NO− to FeIII. The EPR (electron paramagnetic resonance) spectra of the SNAP- and gaseous NO-treated porphyrins were obtained and compared. The difference between the spectra of the cationic and anionic porphyrins indicates different local symmetry and Fe–N–O bond angle. SNAP-treatment produced much more resolved hyperfine structures than gaseous NO-treatment.