Diiron N-bridged species bearing phthalocyanine ligand catalyzes oxidation of methane, propane and benzene under mild conditions

被引:48
作者
Kudrik, Evgeny V. [1 ]
Afanasiev, Pavel [1 ]
Bouchu, Denis [2 ]
Millet, Jean-Marc M. [1 ]
Sorokin, Alexander B. [1 ]
机构
[1] Univ Lyon 1, CNRS, Inst Rech Catalyse & Environm Lyon, IRCELYON,UMR 5256, F-69626 Villeurbanne, France
[2] Univ Lyon 1, Ctr Commun Spectrometrie Masse, UMR 5246, F-69622 Villeurbanne, France
关键词
methane; benzene; oxidation; catalysis; phthalocyanine; diiron oxo complex; hydrogen peroxide; NIH shift; O-18; labeling;
D O I
10.1142/S1088424608000431
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Transformation of methane, the most abundant and the least reactive compound of natural gas to valuable products is one of the most difficult chemical problems of great practical importance. In Nature, methane monooxygenase enzymes transform methane to methanol in water under physiological conditions. However, chemical analogs for such a transformation are unknown. Here, we show the mild and efficient aqueous oxidation of methane by hydrogen peroxide, an ecologically and biologically relevant oxidant catalyzed by supported mu-nitrido diiron phthalocyanine dimer, ((FePcBu4)-Bu-t)(2)N. This bio-inspired complex containing a stable Fe-N-Fe motif catalyzes the oxidation of methane to methanol which is further transformed to formaldehyde and formic acid as is demonstrated using, (CH4)-C-13 and O-18 labelling. ((FePcBu4)-Bu-t)(2)N-H2O2 system shows a high activity in the oxidation of benzene to phenol which occurs via formation of benzene oxide and exhibits NIH shift typically accociated with biological oxidation. Mechanistic features of oxidation of methane and benzene as well as detected inter-mediate hydroperoxo- and high valent oxo diiron complexes support an O-atom transfer reaction mechanism relevant to bio-oxidation. Copyright (C) 2008 Society of Porphyrins & Phthalocyanines.
引用
收藏
页码:1078 / 1089
页数:12
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