ACS Catalysis p. 39 - 44 (2015)
Update date:2022-08-05
Topics:
Ottenbacher, Roman V.
Talsi, Evgenii P.
Bryliakov, Konstantin P.
The mechanism of selective oxidation of aliphatic C-H groups with H2O2 in the presence of aminopyridine Mn complexes, modeling the reactivities of natural oxygenases of the cytochrome P450 superfamily, has been examined. The oxygenation of C-H groups proceeds via hydrogen atom abstraction by the electrophilic metal site; the logarithm of C-H oxidation rates correlates linearly with bond dissociation energies for homolytic C-H bond cleavage. Hammett correlations and stereospecificity studies reflect the formation of a short-lived electron-deficient radical intermediate. Isotopic labeling studies confirm the incorporation of 18O from added H218O, thus providing so far lacking evidence for the oxomanganese(V)-mediated oxidation mechanism. (Figure Presented).
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