Alkali-metal trichloroacetates for dichloromethylenation of fullerenes: nucleophilic addition-substitution route.

Autor: Apenova MG; Chemistry Department M. V. Lomonosov Moscow State University, Leninskie Gory, 1, 119991, Moscow (Russia), Fax: (+7) 495 939 1240., Akhmetov VA, Belov NM, Goryunkov AA, Ioffe IN, Lukonina NS, Markov VY, Sidorov LN
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2014 Mar; Vol. 9 (3), pp. 915-23. Date of Electronic Publication: 2013 Dec 27.
DOI: 10.1002/asia.201301413
Abstrakt: 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 .
(Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje