Stepwise Regioselective Hydrogenation of cis-2-C₆₀(CF₂)₂ Homofullerene with [6,6]-Open/Closed Valence Tautomerism

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• 作者：Viktor P. Bogdanov ; Olesya O. Semivrazhskaya ; Nikita M. Belov ; Prof. Dr. Sergey I. Troyanov ; Dr. Vitaliy Yu. Markov ; Dr. Ilya N. Ioffe ; Prof. Dr. Erhard Kemnitz and Dr. Alexey A. Goryunkov
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：October 17, 2016
• 年：2016
• 卷：22
• 期：43
• 页码：15485-15490
• 全文大小：1173K
• ISSN：1521-3765

文摘

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)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 C₆₀(CF₂)₂H₂ and [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.