One-electron reduction of ferrideuterioporphyrin IX and reaction of the oxidized and reduced forms with chlorinated methyl radicals

Model Studies in Cytochrome P-450-Mediated Toxicity of Halogenated Compounds: Radical Processes Involving Iron Porphyrins

“…With appropriate choice of concentrations, half the reducing radicals may be used to produce iron(II) porphyrin according to: (31,35). The remaining radicals are converted to the alkyl radicals as above.…”

“…On the other hand, reactions of the 'CClI or CF3CHCl radicals with ferrous cytochrome P-450 would be fast. Further reduction of a carbon-halogen bond might lead to the :CC12 or CF3CH2 carbenes (26,35). The :CC12 carbene has been detected by trapping techniques (49) but in very small amounts, suggesting a marginal process.…”

Model studies in cytochrome P-450-mediated toxicity of halogenated compounds: radical processes involving iron porphyrins.

“…The reactions of iron(III) porphyrins with CCl3, CF3CHCl, or CH3 radicals are easily investigated by pulse irradiating the previously mentioned deaerated porphyrin solutions containing a large excess of the appropriate halogenated alkane. Results reported in Table 1 show that CC13 (35) and CF3CHCl (32) radicals react very slowly, if at all, with the ferric complex (the uncertainty on the lower limit of the reaction rate is inherent in the short life of the radicals which decay via self-reaction). The reactivity of alkyl radicals towards ferric porphyrins drastically depends on the nature of carbon substituents.…”

Applications of Flash Spectroscopy to Molecules of Biological Relevance

“…There have been many studies of Hb and M b by flash photolysis, (for example [ 14,27,34,35,44,64,77,88]) and also by time resolved resonance Raman spectroscopy, (for example [97,99,1031). In addition there have also been several studies of protohaem and related iron-porphyrins as models systems, for example [5, 9,19,22,98].…”