期刊
ACS CATALYSIS
卷 5, 期 5, 页码 2702-2707出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.5b00169
关键词
bioinspired catalysis; enantioselective epoxidation; EPR; iron; mechanism
资金
- Russian Scientific Foundation [14-13-00158]
- Russian Science Foundation [14-13-00158] Funding Source: Russian Science Foundation
Herein, we report the EPR spectroscopic study of the bioinspired catalyst systems for selective hydrocarbon oxofunctionalizations based on dinuclear ferric complexes with TPA* and PDP* aminopyridine ligands, hydrogen peroxide, and acetic acid (TPA* = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine, PDP* = bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2'-bipyrrolidine). Using very low temperatures, -75 to -85 degrees C, the extremely unstable and reactive ironoxygen intermediates, directly reacting with olefins even at -85 degrees C, have been detected for the first time. Their EPR parameters (g(1) = 2.070-2.071, g(2) = 2.005-2.008, g(3) = 1.956-1.960) were very similar to those of the known oxoiron(V) complex [(TMC)Fe-V-O(NC(O)CH3)](+) (g(1) = 2.053, g(2) = 2.010, g(3) = 1.971, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). On the basis of EPR and reactivity data, the detected intermediates were assigned to the Fe-V=O active oxidizing species of the catalyst systems studied.
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