Stepwise Regioselective Hydrogenation of cis-2-C 60 (CF 2 ) 2 Homofullerene with [6,6]-Open/Closed Valence Tautomerism.

Autor: Bogdanov VP; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia., Semivrazhskaya OO; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia., Belov NM; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia., Troyanov SI; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia., Markov VY; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia., Ioffe IN; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia., Kemnitz E; Institute of Chemistry, Humboldt University Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany., Goryunkov AA; Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia. aag@thermo.chem.msu.ru.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2016 Oct 17; Vol. 22 (43), pp. 15485-15490. Date of Electronic Publication: 2016 Sep 08.
DOI: 10.1002/chem.201602351
Abstrakt: The homofullerene compound cis-2-C 60 (CF 2 ) 2 , which has an unusual kind of open/closed valence tautomerism undergoes consecutive regioselective hydrogenation at bridgehead carbon atoms upon reduction with Zn/Cu couple in H 2 O-toluene mixture. The tautomerism barrier in cis-2-C 60 (CF 2 ) 2 is negligible in the neutral state, whereas negative charging both impedes tautomeric transformation and promotes regioselective addition of electrophilic species at the bridgehead carbon atoms. In light of this observation, two novel homofullerene derivatives, mixed [6,6]-open/closed C 60 (CF 2 ) 2 H 2 and [6,6]-open cis-2-C 60 (CF 2 ) 2 H 4 , were synthesized and their structures were unambiguously determined by means of single crystal X-ray crystallography and NMR spectroscopy.
(© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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