Reductive electrocatalytic dehalogenation of nitrobenzyl halides: nitrophilic or halophilic attack?статья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Аннотация:Electrochemical reduction of Cp2TiCl2 in the presence of benzylic halides results in their catalytic dehalogenation to form toluene derivatives. Possible schemes for the process were proposed on the basis of the results of electrochemical studies and digital simulation data. The catalytic scheme including the halophilic attack of the Ti-III complex to organic halide as a key step occurs for unsubstituted benzylic halides. In the case of nitro-substituted substrates, the reaction is strongly accelerated. In this case, an electron transfer from the reduced form of the catalyst to the NO2 group of organic halide is possibly accompanied by the intramolecular charge transfer to the C-Hal bond, thus facilitating its cleavage. Thus, the nitro group in the starting benzylic halide acts as a "redox antenna," transferring an electron to the C-Hal bond. The proposed scheme is supported by semiempirical calculations of the geometry of molecular complexes with the Ti-Hal or Ti-NO2 coordination.