Chlorination-Promoted Skeletal-Cage Transformations of C88 Fullerene by C2 Losses and a C-C Bond Rotation

Shangfeng Yang; Tao Wei; Kerstin Scheurell; Erhard Kemnitz; Sergey I Troyanov

doi:10.1002/chem.201501549

Chlorination-Promoted Skeletal-Cage Transformations of C88 Fullerene by C2 Losses and a C-C Bond Rotation

Chemistry. 2015 Oct 19;21(43):15138-41. doi: 10.1002/chem.201501549. Epub 2015 Sep 1.

Authors

Shangfeng Yang¹, Tao Wei², Kerstin Scheurell³, Erhard Kemnitz⁴, Sergey I Troyanov⁵

Affiliations

¹ CAS Key Laboratory of Materials for Energy Conversion & Department of Material Science and Engineering, University of Science and Technology of China (USTC), Hefei, 230026 (P. R. China). sfyang@ustc.edu.cn.
² CAS Key Laboratory of Materials for Energy Conversion & Department of Material Science and Engineering, University of Science and Technology of China (USTC), Hefei, 230026 (P. R. China).
³ Institute of Chemistry, Humboldt University of Berlin, Brook-Taylor-Str. 2, 12489 Berlin (Germany).
⁴ Institute of Chemistry, Humboldt University of Berlin, Brook-Taylor-Str. 2, 12489 Berlin (Germany). erhard.kemnitz@chemie.hu-berlin.de.
⁵ Chemistry Department, Moscow State University, 119991 Moscow, Leninskie gory (Russia). stroyano@thermo.chem.msu.ru.

PMID: 26332709
DOI: 10.1002/chem.201501549

Abstract

High-temperature chlorination of fullerene C88 (isomer 33) with VCl4 gives rise to skeletal transformations affording several nonclassical (NC) fullerene chlorides, C86 (NC1)Cl24/26 and C84 (NC2)Cl26 , with one and two heptagons, respectively, in the carbon cages. The branched skeletal transformation including C2 losses as well as a Stone-Wales rearrangement has been comprehensively characterized by the structure determination of two intermediates and three final chlorination products. Quantum-chemical calculations demonstrate that the average energy of the C-Cl bond is significantly increased in chlorides of nonclassical fullerenes with a large number of chlorinated sites of pentagon-pentagon adjacency.

Keywords: DFT calculations; cage transformations; chlorination; fullerenes; structure elucidation.