Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations

Williamson N. Oloo, Katlyn K. Meier, Yong Wang, Sason Shaik, Eckard Münck and Lawrence Que ()
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Williamson N. Oloo: University of Minnesota
Katlyn K. Meier: Carnegie Mellon University
Yong Wang: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Sason Shaik: The Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem
Eckard Münck: Carnegie Mellon University
Lawrence Que: University of Minnesota

Nature Communications, 2014, vol. 5, issue 1, 1-9

Abstract: Abstract Synthetically useful hydrocarbon oxidations are catalysed by bio-inspired non-heme iron complexes using hydrogen peroxide as oxidant, and carboxylic acid addition enhances their selectivity and catalytic efficiency. Talsi has identified a low-intensity g=2.7 electron paramagnetic resonance signal in such catalytic systems and attributed it to an oxoiron(V)-carboxylate oxidant. Herein we report the use of FeII(TPA*) (TPA*=tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) to generate this intermediate in 50% yield, and have characterized it by ultraviolet–visible, resonance Raman, Mössbauer and electrospray ionization mass spectrometric methods as a low-spin acylperoxoiron(III) species. Kinetic studies show that this intermediate is not itself the oxidant but decays via a unimolecular rate-determining step to unmask a powerful oxidant. The latter is shown by density functional theory calculations to be an oxoiron(V) species that oxidises substrate without a barrier. This study provides a mechanistic scenario for understanding catalyst reactivity and selectivity as well as a basis for improving catalyst design.

Date: 2014
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DOI: 10.1038/ncomms4046

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