Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins

Journal Article · Fri May 27 00:00:00 EDT 1994 · Science (Washington, D.C.); (United States)

DOI:https://doi.org/10.1126/science.8191283· OSTI ID:6981094

Grinstaff, M W; Hill, M G; Labinger, J A; Gray, H B ^[1]

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1. California Institute of Technology, Pasadena, CA (United States)

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 perhalogenated iron(II) porphyrins such as Fe(TFPPBr[sub 8]) [H[sub 2]TFPPBr[sub 8], [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(TFPPBr[sub 8])Cl occurs through a radical-chain mechanism in which the radicals are generated by oxidation and reduction of alkyl hydroperoxides.

• OSTI ID: 6981094
• Journal Information: Science (Washington, D.C.); (United States), Journal Name: Science (Washington, D.C.); (United States) Vol. 264:5163; ISSN SCIEAS; ISSN 0036-8075
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROPEROXY RADICALS
IRON COMPLEXES
KINETICS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PORPHYRINS
RADICALS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES