Inspired by the versatile oxidation chemistry catalyzed by nonheme iron enzymes, we have been investigating hydrocarbon oxidations by H2O2 that are catalyzed by nonheme iron complexes of neutral tetradentate ligands. Acetic acid (AcOH) has been shown to increase the efficiency and selectivity of these catalysts.1 Mechanistic investigations into the role of this additive reveal the involvement of an iron(III)-acylperoxo intermediate, which is different from the iron(III)-hydroperoxo species that is formed in the absence of AcOH.2,3 Kinetic studies show that both intermediates undergo rate determining decay to unmask oxoiron(V) oxidants that carry out the oxidative transformations. Our studies on the evolution of these intermediates in catalytic hydrocarbon oxidation reactions will be presented. White, M. C., Adding Aliphatic C-H Bond Oxidations to Synthesis Science 2012 , 335, 807-809.Oloo, W. N.; Meier, K. K.; Wang, Y.; Shaik, S.; M�nck, E.; Que, L., Jr., Identification of a Low-spin Acylperoxoiron(III) Intermediate in Bio-inspired Nonheme Iron-Catalyzed Oxidations Nature Communications 2014 , DOI: 10.1038/ncomms4046.Oloo, W. N.; Fielding, A. J.; Que, L., Jr., Rate Determining Water-Assisted O�O Bond Cleavage of a FeIII�OOH Intermediate in a Bio-inspired Nonheme Iron-Catalyzed Oxidation J. Am. Chem. Soc. 2013 , 135, 6438-6441.

Hydrocarbon oxidations by bio-inspired nonheme iron catalysts

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.