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Detection of alkylperoxo and ferryl, (Fe sup IV = O) sup 2+ , intermediates during the reaction of tert-butyl hydroperoxide with iron porphyrins in toluene solution

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00202a021· OSTI ID:6708519
PFe{sup II} and PFe{sup III}OH (P is a porphyrin dianion) catalyze the decomposition of tert-butyl hydroperoxide in toluene solution without appreciable attack on the porphyrin ligand. {sup 1}H NMR spectroscopic studies at low temperature ({minus}70{degree}C) give evidence for the formation of a high-spin, five-coordinate intermediate, PFe{sup III}OOC(CH{sub 3}){sub 3}. Organic products formed from this reaction are tert-butyl alcohol, di-tert-butyl peroxide, benzaldehyde, acetone, and benzyl-tert-butyl peroxide, which arise largely from a radical chain process initiated by the iron porphyrin but continuing without its intervention.
OSTI ID:
6708519
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:20; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English