Science 1994-05-27

Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins.

M W Grinstaff, M G Hill, J A Labinger, H B Gray

文献索引：Science 264(5163) , 1311-3, (1994)

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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.