Alkali-Metal Trichloroacetates for Dichloromethylenation of Fullerenes: Nucleophilic Addition-Substitution Routeстатья
Статья опубликована в высокорейтинговом журнале
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 16 апреля 2014 г.
Аннотация:The first experimental evidence that fullerenes react with alkali-metal trichloroacetates through a nucleophilic addition-substitution route, yielding dichloromethylenefullerenes as the final products, is reported. The intermediates, C60(CCl3)− and C70(CCl3)− anions, have been isolated in their protonated forms as ortho-C60(CCl3)H, as well as three ortho and one para isomer of C70(CCl3)H. The structures were unambiguously determined by means of 1H, 13C, and 1H–13C HMBC NMR spectroscopy along with UV/Vis spectroscopy. The observed regiochemistry was analyzed with the aid of quantum chemical calculations. Conversion of the protonated compounds into the [6,6]-closed C60/70(CCl2) cycloadducts under basic conditions can be effected only for the ortho isomers, whereas para-C70(CCl3)H decomposes back into pristine C70.