The development of catalysts that employ earth abundant metals to achieve controlled oxidation of strong C-H bonds using O2 has been a continued challenge in the inorganic chemistry community. This is due to the preference for homolytic rather than heterolytic cleavage of the O-O bond which gives rise to the production of freely diffusing radicals, making selective C-H bond oxidation challenging. The mononuclear non-heme iron(II) catalyst, [FeII(N2O1)(α-ketoacid)] (N2O1 is 2-((2-(dimethylamino)ethyl)(methyl)amino)-acetic acid), has been shown to catalytically promote the cleavage of the dioxygen bond to generate a metal-bound oxidant without the formation of freely diffusing oxygen based radicals. The kinetics of the reaction of [FeII(N2O1)(α-ketoacid)] with O2 in methanol has been investigated by variable low-temperature stopped-flow spectroscopy in order to develop a mechanistic model for the catalytic cycle. A discussion of the number of kinetically identified intermediates, their potential identities, and progress in their characterization by spectroscopic (MCD, Mössbauer, and EPR) and computational (DFT) methodologies will be presented. Insight from these mechanistic studies will further our understanding of O2 activation at a single metal center and allow for the design of new catalysts that can selectively oxidize C-H bonds via oxygen insertion and/or rebound pathways.

Kinetic and spectroscopic investigation of oxygen activation at a single iron center via Gibbs free energy coupling: Generation of an active alkane oxidation catalyst

256th National Meeting (2018)

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