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Stepwise Regioselective Hydrogenation of cis ‐2‐C 60 (CF 2 ) 2 Homofullerene with [6,6]‐Open/Closed Valence Tautomerism
Author(s) -
Bogdanov Viktor P.,
Semivrazhskaya Olesya O.,
Belov Nikita M.,
Troyanov Sergey I.,
Markov Vitaliy Yu.,
Ioffe Ilya N.,
Kemnitz Erhard,
Goryunkov Alexey A.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201602351
Subject(s) - tautomer , regioselectivity , chemistry , valence (chemistry) , electrophile , toluene , crystallography , stereochemistry , medicinal chemistry , catalysis , organic chemistry
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.