Identification of intermediates and products in the reaction of porphyrin iron(III) alkyl complexes with dioxygen
Unlike most PFe/sup III+/ (P is a porphyrin dianion) complexes, complexes of the type PFe/sup III/CH/sub 2/R (R = H or CH/sub 3/) are reactive toward dioxygen with the ubiquitous PFe/sup III/O-Fe/sup III/P as the only reported product. Here the authors report on /sup 1/H NMR studies of this reaction which focus on the detection of intermediates and the fate of the alkyl group. These results should be viewed in the context of extensive previous studies on model systems for dioxygen activation in biological systems (heme oxygenases) involving reaction of dioxygen with PFe/sup II/ and on the interaction of peracids and hydroperoxides with PFe/sup III/. Through these studies a number of reactive intermediates including the peroxobridge complex, PFe/sup III/-O-O-Fe/sup III/P, and the ferryl complexes, PFe/sup IV/ double bond O, (B)P-Fe/sup IV/ double bond O (B is an amine), and (P)Fe/sup IV/ double bond O/sup +/ (P is a porphyrin radical monoanion), have been detected.
- Research Organization:
- Univ. of California, Davis
- OSTI ID:
- 5890798
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKANES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
IRON COMPLEXES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NMR SPECTRA
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN
PORPHYRINS
REACTION INTERMEDIATES
RESONANCE
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES