A common heterolytic mechanism for reactions of iodosobenzenes, peracids, hydroperoxides, and hydrogen peroxide with iron(III) porphyrins
- Univ. of California, San Diego, La Jolla (USA)
The isolation of high-valent iron porphyrin intermediates, kinetic studies, and product isolations have demonstrated that the principal reaction of iron(III) porphyrins with iodosobenzenes and peracids is a two-electron oxidation to the iron(IV) radical cation (oxene). It is clear that the Fe(IV) and Fe(III) species are readily obtainable by electron-transfer reactions. However, production of the oxene Fe{sup +}=O through the endothermic reversal of such electron transfers is highly unlikely. Therefore the identification of products exclusively derived from the oxene should serve as an indication of heterolytic cleavage in the first step. We submit demonstrations of the presence of Fe{sup +}=O. We have found that the epoxidation of norbornene by use of the oxene produces a mixture of products which, is at once unlike that from any other epoxidation process and specific for the particular metalloporphyrin catalyst.
- OSTI ID:
- 6707203
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 111:20; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
59 BASIC BIOLOGICAL SCIENCES
PEROXIDES
CHEMICAL REACTION KINETICS
PORPHYRINS
CALCULATION METHODS
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
IRON
MEASURING INSTRUMENTS
MEASURING METHODS
CARBOXYLIC ACIDS
DATA
ELEMENTS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
METALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENTS
400500* - Photochemistry
400400 - Electrochemistry
550000 - Biomedical Sciences
Basic Studies