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Addition of CF2 group to endohedral fullerene Sc3N@Ih-C80

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Abstract

We report the first successful synthesis of a CF2 derivative of the stable endohedral fullerene Sc3N@Ih-C80. Reaction with CF2ClCOONa yields a single Cs-symmetric Sc3N@C80(CF2) adduct where the CF2 group is inserted into a [6,6]-bond and opens it to 2.3 Å between the bridgehead carbon atoms. As evidenced by absorption and fluorescence spectroscopy as well as cyclic voltammetry, both the HOMO and the LUMO level of Sc3N@C80(CF2) are slightly (ca. 0.1 eV) downshifted with respect to the parent Sc3N@Ih-C80, so the HOMO–LUMO gap remains essentially unchanged. The DFT calculations suggest that the reaction mechanism is not the previously assumed [2 + 1]-cycloaddition of :CF2 carbene but rather nucleophilic addition of CF2Cl anion followed by elimination of Cl and closing of the CF2 bridge via intramolecular nucleophilic substitution. Selective formation of the [6,6]-Sc3N@C80(CF2) turns out to be kinetically controlled and promoted by a particular orientation of the endohedral Sc3N cluster with respect to the CF2Cl addition site. In its turn, the CF2 addend partly hampers the rotation of Sc3N the endohedral cluster compared to its quasi-free reorientations in the parent Sc3N@Ih-C80.

Graphical abstract: Addition of CF2 group to endohedral fullerene Sc3N@Ih-C80

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Supplementary files

Article information


Submitted
25 Apr 2020
Accepted
13 Jun 2020
First published
15 Jun 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Addition of CF2 group to endohedral fullerene Sc3N@Ih-C80

A. D. Pykhova, O. O. Semivrazhskaya, N. A. Samoylova, A. V. Rybalchenko, M. Rosenkranz, I. N. Ioffe, A. A. Popov and A. A. Goryunkov, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT01513J

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