Premium
CF 2 ‐Functionalized Trifluoromethylated Fullerene C 70 (CF 3 ) 8 (CF 2 ): Structure, Electronic Properties, and Spontaneous Oxidation at the Bridgehead Carbon Atoms
Author(s) -
Lukonitalia S.,
Semivrazhskaya Olesya O.,
Apenova Marina G.,
Belov Nikita M.,
Troyanov Sergey I.,
Goryunkov Alexey A.
Publication year - 2019
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201900475
Subject(s) - chemistry , carbene , nucleophile , cyclopropanation , homo/lumo , stereochemistry , medicinal chemistry , photochemistry , crystallography , molecule , catalysis , organic chemistry
Thermally‐induced CF 2 addition to C s ‐C 70 (CF 3 ) 8 upon reaction with sodium chlorodifluoroacetate is found to proceed via the nucleophilic cyclopropanation pathway, possibly with a certain involvement of the alternative singlet carbene pathway. Of the two major isomers of C 70 (CF 3 ) 8 (CF 2 ) characterized by X‐ray diffraction and spectroscopically, the less abundant one has a [6,6]‐open structure whereas the more abundant product is a [5,6]‐open isomer with highly reactive bridgehead sites. Under ambient conditions, its rapid oxidation and hydration produce C 70 (CF 3 ) 8 [CF 2 ](OH) 2 and C 70 (CF 3 ) 8 [CF 2 ](OH)H, respectively, in which the π‐system is split in two disjoint caps and the HOMO–LUMO gap is considerably increased, as evidenced by the blue‐shifted fluorescence.