Stepwise Regioselective Hydrogenation of cis-2-C60(CF2)2Homofullerene with [6,6]-Open/Closed Valence Tautomerism.
The homofullerene compound cis-2-C60(CF2)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 H2O-toluene mixture. The tautomerism barrier in cis-2-C60(CF2)2is 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 C60(CF2)2H2and [6,6]-open cis-2-C60(CF2)2H4, were synthesized and their structures were unambiguously determined by means of single crystal X-ray crystallography and NMR spectroscopy.
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Viktor P
VP
Bogdanov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Olesya O
OO
Semivrazhskaya
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Nikita M
NM
Belov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Sergey I
SI
Troyanov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Vitaliy Yu
VY
Markov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Ilya N
IN
Ioffe
Institute of Chemistry, Humboldt University Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany.
Erhard
E
Kemnitz
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia. aag@thermo.chem.msu.ru.
Alexey A
http://orcid.org/0000-0003-4460-5370
AA
Goryunkov
fullerenes; hydrogenation; regioselectivity; structure elucidation; tautomerism