Journal of the American Chemical Society p. 1477 - 1483 (1989)
Update date:2022-08-11
Topics:
Balasubramanian, P. N.
Lindsay Smith, John R.
Davies, Michael J.
Kaaret, Thomas W.
Bruice, Thomas C.
The reaction of t-BuOOH with the water soluble and non-μ-oxo dimer forming (5,10,15,20-tetrakis(2,6-dimethyl-3-sulfonatophenyl)porphinato)iron(III) hydrate ((1)FeIII(X)(H2O) where X=H2O or HO(1-)) was studied in aqueous solution between pH 2 and 13 in the absence of an agent for the trapping of reaction intermediates.Products of t-BuOOH decomposition are (CH3)2CO (90percent), CH3OH (90percent), and t-BuOH (15percent), while neither CH4, C2H6, O2, nor (t-BuO)2 could be detected.That (CH3)2CO and CH3OH are formed through fragmentation of t-BuO. to (CH3)2CO and CH3. is shown by theobservation that the reaction of Ph(CH3)2COOH with (1)FeIII(X)(H2O) provides acetophenone but not phenol.This must be a consequence of homolytic O-O bond scission with the formation of Ph(CH3)2CO..The reaction of (1)FeIII(X)(H2O) with m-ClC6H4CO3H and the hydroperoxides t-BuOOH, Ph(CH3)2COOH, Ph2C(CO2CH3)OOH, and Ph2C(CN)OOH between pH 5 and 7 leads to the buildup of (1)FeIV(X)(H2O) species.The formation of an iron(IV)-oxo porphyrin species was established by titrimetric experiments as well as by carbon microelectrode voltommetry and 1e(1-) spectroelectrochemical generation of authentic (1)FeIV(X)(H2O) species.Formation of (1)FeIV(X)(H2O) species on oxidation of (1)FeIII(X)(H2O) with m-ClC6H4CO3H occurs in the absence of O2, while formation of (1)FeIV(X)(H2O) species on oxidation of (1)FeIII(X)(H2O) by the alkyl hydroperoxides, t-BuOOH and Ph(CH3)2COOH, requires the presence of O2.These observations require for the peracid a 2e(1-) oxidation with heterolytic O-O bond cleavage
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