Reduction-Induced o-C–H Bond Activation of Pyridine with Decamethylzirconocene Dichlorideстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Аннотация:Treatment of decamethylzirconocene dichloride (h5-Cp*)2ZrCl2 with amalgamated magnesium in pyridine results in formation of the o-C–H bond activation product [h5-C5Me5]2ZrH[h2-kC,N-C5H4N] (1). X-ray diffraction analysis (solid state) and NMR spectroscopy data (solutions) reveal the lateral positioning of the nitrogen atom in 1. At elevated temperatures, complex 1 smoothly rearranges into its isomer 2 with medial positioning of the N-atom. The parameters of equilibrium between 1 and 2 were measured at different temperatures. A reaction of 1 or a mixture of 1 and 2 (ca. 1:10) with CDCl3 smoothly and under mild conditions leads to one and the same h2-pyridyl chloride complex [h5-C5Me5]2ZrCl[h2-kC,N-C5H4N] (3) with medial positioning of the N-atom. The thermodynamic and mechanistic concepts of the paper are discussed with application of the DFT computational data.