期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 19, 页码 3009-3019出版社
WILEY-BLACKWELL
DOI: 10.1002/ejic.200800156
关键词
cobalt; porphyrinoids; azides; homogeneous catalysis; C-H activation
Co(II)(tpp) catalyzes the reaction of aromatic azides (ArN(3)) with nonactivated olefins to yield allylic amines or aziridines in moderate-to-good yields. The chemoselectivity of the catalytic reaction is particularly high. Depending on the substrate employed, allylic amines or aziridines can be obtained. The reaction mechanism was investigated, and the reaction proceeds through reversible coordination of the aryl azide to the Coll-porphyrin complex. The often postulated nitrene complex is not an intermediate in this reaction. The kinetics for the allylic amination is first order in azide, Co(tpp), and olefin. For the aziridination, the kinetics is again first order in azide and catalyst, but we observed a first-order dependence of the rate on a-methylstyrene only up to an olefin concentration of 6.9 m. An inhibiting role of the competitively formed 1-(4-nitrophenyl)-5-methyl-5-phenyl-1,2,3-triazoline was identified. The triazoline was shown to reversibly coordinate to Co(tpp), which blocks the free coordination site necessary for the catalytic reaction to proceed, and is it responsible for the catalyst deactivation in the aziridination reaction of a-methylstyrene by 4-nitrophenyl azide. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
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