Mechanisms of reactions of iron(III) porphyrins with hydrogen peroxide and hydroperoxides: Solvent and solvent isotope effects

Journal Article · Wed Jan 03 04:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00157a029· OSTI ID:6652546

Traylor, T G; Xu, Feng ^[1]

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1. Univ. of California, San Diego, La Jolla (USA)

The effect of solvent polarity and acidity and the solvent isotope effects on the reaction of iron(III) porphyrins with hydrogen peroxide, tert-butyl hydroperoxide, and peracids have been investigated. Both the solvent isotope effects on the reactions of hydroperoxides with hemins are almost identical with these effects on the reactions of hydroperoxides with dialkyl sulfides and the effects on the reaction of peracids with iron(III) porphyrins. Since both of the latter reactions are known to involve heterolytic cleavage of the O-O bond, this similarity provides strong evidence for heterolytic cleavage of hydroperoxide by reaction with hemins. The strong alcohol catalysis of the studied reactions provides a mechanistic rationale for the O-O bond cleavage in cytochrome P-450 in terms of general-acid catalysis by water in the enzyme site.

• OSTI ID: 6652546
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:1; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500 -- Photochemistry
CARBOXYLIC ACIDS
CHEMICAL REACTION KINETICS
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
INFORMATION
ISOTOPE EFFECTS
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PORPHYRINS
REACTION KINETICS
SOLVENT PROPERTIES