Abstract
The mechanism of the dioxygenation of 3-methyl- indole occurring in the presence of Fe(III)TPPCl and alkaline reagents was studied by means of product analyses and spectroscopic measurements. The results of GC-MS measurements indicated that 3-methyl- indole (skatole) was converted to o-formamidoacetophenone (FA), in which two oxygen atoms derived from atmospheric oxygen were involved. The optical spectrum recorded for the mixture at −78°C demonstrated the presence of a new iron complex as characterized by absorption maxima at 421, 550 and 586 nm. The ESR spectrum recorded for the same reaction mixture revealed the formation of two types of ferric low-spin complexes ( g 1 = 2.32, g 2 = 2.17, g 3 = 1.95; g 1 =2.24, g 2 =2.16, g 3 = 1.96) with anomalously small g anisotropy. From comparison of ESR parameters of the complexes with those of previously reported heme-butyl peroxide complexes, the present complexes were assumed to be the six- coordinate Fe(III)TPP-peroxide complex. Based on superhyperfine splittings (27 gauss) derived from 17O 2 enriched oxygen ( 17O 2, I= 5/2), these complexes were concluded to be the Fe(III)TPP( −OCH 3)- ( −OO-skatole) and Fe(III)TPP( −OO-skatole) 2 complexes, having 3-methyl-3-hydroperoxo-indolenine at the axial position. The Fe(III)TPP-oxygen-substrate ternary complex will be an important intermediate species generated in the dioxygenation processes of skatole.
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