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Nonheme Iron‐Oxo‐Catalyzed Methane Formation from Methyl Thioethers: Scope, Mechanism, and Relevance for Natural Systems
Author(s) -
Benzing Kathrin,
Comba Peter,
Martin Bodo,
Pokrandt Bianca,
Keppler Frank
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701986
Subject(s) - chemistry , methane , catalysis , methanol , demethylation , methyl formate , thioether , radical , sulfone , formate , organic chemistry , medicinal chemistry , biochemistry , gene expression , dna methylation , gene
A range of nonheme oxo‐iron(IV) model systems with tetra‐ or pentadentate ligands is shown to produce methane from methionine and other thioethers. This model reaction for the natural aerobic production of methane is shown to proceed via two sulfoxidation steps involving the oxo‐iron(IV) complexes, with a bifurcation in the second step that either produces the sulfone or leads to demethylation with similar probabilities. In the presence of O 2 , the resulting methyl radicals produce methanol and formate or, in an O 2 ‐depleted environment, lead to formation of methane.