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Catalytic H2O2 Activation by a Diiron Complex for Methanol Oxidation.
Zimmermann, Thomas Philipp; Orth, Nicole; Finke, Sebastian; Limpke, Thomas; Stammler, Anja; Bögge, Hartmut; Walleck, Stephan; Ivanovic-Burmazovic, Ivana; Glaser, Thorsten.
Affiliation
  • Zimmermann TP; Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany.
  • Orth N; Department Chemie und Pharmazie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, D-91058 Erlangen, Germany.
  • Finke S; Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany.
  • Limpke T; Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany.
  • Stammler A; Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany.
  • Bögge H; Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany.
  • Walleck S; Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany.
  • Ivanovic-Burmazovic I; Department Chemie und Pharmazie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, D-91058 Erlangen, Germany.
  • Glaser T; Department Chemie, Ludwigs-Maximilians-Universität, Butenandtstraße 5-13, 81377 München, Germany.
Inorg Chem ; 59(21): 15563-15569, 2020 Nov 02.
Article in En | MEDLINE | ID: mdl-33081463
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.

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Inorg Chem Year: 2020 Document type: Article Affiliation country: Germany Country of publication: United States

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Inorg Chem Year: 2020 Document type: Article Affiliation country: Germany Country of publication: United States