- Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins.
Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins.
Science (New York, N.Y.) (1994-05-27)
M W Grinstaff, M G Hill, J A Labinger, H B Gray
PMID8191283
摘要
Halogenation of an iron porphyrin causes severe saddling of the macrocyclic structure and a large positive shift in the iron(III)/(II) redox couple. Although pre-halogenated iron(II) porphyrins such as Fe(TFPPBr8) [H2TFPPBr8, beta-octabromo-tetrakis(pentafluorophenyl)-porphyrin] are relatively resistant to autoxidation, they rapidly reduce alkyl hydroperoxides. These and related reactivity studies suggest that catalysis of alkane oxygenation by Fe(TFPPBr8)Cl occurs through a radical-chain mechanism in which the radicals are generated by oxidation and reduction of alkyl hydroperoxides.