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

被引：12

作者：

Bogdanov, Viktor P. ^{[1
]}

Semivrazhskaya, Olesya O. ^{[1
]}

Belov, Nikita M. ^{[1
]}

Troyanov, Sergey I. ^{[1
]}

Markov, Vitaliy Yu. ^{[1
]}

Ioffe, Ilya N. ^{[1
]}

Kemnitz, Erhard ^{[2
]}

Goryunkov, Alexey A. ^{[1
]}

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Leninskie Gory 1-3, Moscow 119991, Russia

[2] Humboldt Univ, Inst Chem, Brook Taylor Str 2, D-12489 Berlin, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 43期

基金：

俄罗斯基础研究基金会;

关键词：

fullerenes; hydrogenation; regioselectivity; structure elucidation; tautomerism; CONJUGATED POLYMERS; FULLERENE; METHANOFULLERENES; CHEMISTRY; ACCEPTORS; EXPANSION; C-60(CF2); ADDITIONS; ADDUCTS; CIS-2;

D O I：

10.1002/chem.201602351

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The homofullerene compound cis-2-C-60(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-C-60(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 C-60(CF2)(2)H-2 and [6,6]-open cis-2-C-60(CF2)(2)H-4, were synthesized and their structures were unambiguously determined by means of single crystal X-ray crystallography and NMR spectroscopy.

引用

页码：15485 / 15490

页数：6

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