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Detection of Alkylperoxo and Ferryl, (Fe(IV)=O)(2+), Intermediates during the Reaction of tert-Butyl Hydroperoxide with Iron Porphyrins in Toluene Solution
Arasasingham, Ramesh D.,Cornman, Charles R.,Balch, Alan L.
, p. 7800 - 7805 (2007/10/02)
PFeII and PFeIIIOH (P is a porphyrin dianion) catalyze the decomposition of tert-butyl hydroperoxide in toluene solution without appreciable attack on the porphyrin ligand. (1)H NMR spectroscopic studies at low temperature (-70 deg C) give evidence for the formation of a high-spin, five-coordinate intermediate, PFeIIIOOC(CH3)3.On warming this decomposes to PFeIIIOH (P = tetramesitylporphyrin, TMP) or PFeIIIOFeIIIP (P = tetra-p-tolylporphyrin, TTP) with the formation of (TMP)FeIV=O as an observed intermediate in the first case.Treatment of PFeIIIOOC(CH3)3 at -70 deg C with N-methylimidazole (MeIm) yields the intermediate (MeIm)PFeIV=O.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.
