title: Alkali-metal trichloroacetates for dichloromethylenation of fullerenes: nucleophilic addition-substitution route.
abstract: 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 (1) H, (13) C, and (1) H-(13) C 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 .
authors.affiliation: Chemistry Department M. V. Lomonosov Moscow State University, Leninskie Gory, 1, 119991, Moscow (Russia), Fax: (+7) 495 939 1240.
authors.forename: Marina G
authors.initials: MG
authors.lastname: Apenova
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Akhmetov
authors.forename: Nikita M
authors.initials: NM
authors.lastname: Belov
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Goryunkov
authors.forename: Ilya N
authors.initials: IN
authors.lastname: Ioffe
authors.forename: Natalia S
authors.initials: NS
authors.lastname: Lukonina
authors.forename: Vitaliy Yu
authors.initials: VY
authors.lastname: Markov
authors.forename: Lev N
authors.initials: LN
authors.lastname: Sidorov
keywords: NMR spectroscopy; alkylation; fullerenes; mass spectrometry; reaction mechanisms