Catalytic H2O2 Activation by a Diiron Complex for Methanol Oxidation

Zimmermann TP, Orth N, Finke S, Limpke T, Stammler A, Bögge H, Walleck S, Ivanovic-Burmazovic I, Glaser T (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 59

Pages Range: 15563-15569

Journal Issue: 21

DOI: 10.1021/acs.inorgchem.0c02698

Abstract

In nature, C-H bond oxidation of CH4 involves a peroxo intermediate that decays to the high-valent active species of either a "closed" {FeIV(μ-O)2FeIV} core or an "open" {FeIV(O)(μ-O)FeIV(O)} core. To mimic and to obtain more mechanistic insight in this reaction mode, we have investigated the reactivity of the bioinspired diiron complex [(susan){Fe(OH)(μ-O)Fe(OH)}]2+ [susan = 4,7-dimethyl-1,1,10,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraazadecane], which catalyzes CH3OH oxidation with H2O2 to HCHO and HCO2H. The kinetics is faster in the presence of a proton. 18O-labeling experiments show that the active species, generated by a decay of the initially formed peroxo intermediate [(susan){FeIII(μ-O)(μ-O2)FeIII}]2+, contains one reactive oxygen atom from the μ-oxo and another from the μ-peroxo bridge of its peroxo precursor. Considering an FeIVFeIV active species, a "closed" {FeIV(μ-O)2FeIV} core explains the observed labeling results, while a scrambling of the terminal and bridging oxo ligands is required to account for an "open" {FeIV(O)(μ-O)FeIV(O)} core.

Authors with CRIS profile

Nicole Orth Lehrstuhl für Bioanorganische Chemie Ivana Ivanovic-Burmazovic Lehrstuhl für Bioanorganische Chemie

Involved external institutions

Universität Bielefeld DE Germany (DE)

How to cite

APA:

Zimmermann, T.P., Orth, N., Finke, S., Limpke, T., Stammler, A., Bögge, H.,... Glaser, T. (2020). Catalytic H2O2 Activation by a Diiron Complex for Methanol Oxidation. Inorganic Chemistry, 59(21), 15563-15569. https://doi.org/10.1021/acs.inorgchem.0c02698

MLA:

Zimmermann, Thomas Philipp, et al. "Catalytic H2O2 Activation by a Diiron Complex for Methanol Oxidation." Inorganic Chemistry 59.21 (2020): 15563-15569.

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