Intermediate Products of C60 High‐Temperature Chlorination – C60Cln (n = 8, 10, 14, 20, 24)

• Published in: European journal of organic chemistry Vol. 2020; no. 43; pp. 6801 - 6804
• Main Authors: Tamm, Nadezhda B., Markov, Vitaliy Yu, Goryunkov, Alexey A., Troyanov, Sergey I.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 22.11.2020
• Subjects: Buckminsterfullerene; Cages; Chlorides; Chlorination; Chlorine; Free energy; Fullerenes; Heat of formation; Hydrocarbons; Room temperature; Stoichiometry; Structural analysis; Structure elucidation
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202001260

The products of high‐temperature (440 °C) chlorination of C60 with SbCl5 differ considerably from the products obtained at room temperature because high‐temperature allows for chlorine migration over the fullerene cage. Thus, one can expect to obtain the most favorable chlorination patterns for any C60Cln stoichiometry. We report the isolation and structural characterization of several chlorofullerenes, C2v‐C60Cl8, C1‐C60Cl10, and C1‐C60Cl14, which are intermediates to the more kinetically stable higher chlorides. Theoretical DFT calculations of formation energies verified the high thermodynamic stability of the isolated chlorides. Further chlorination produces Th‐C60Cl24 and, eventually, non‐IPR chlorides, 1805C60Cl24 and 1794C60Cl20. as a result of cage rearrangements. Also isolated is a product of the cage shrinkage, C58Cl20. High‐temperature chlorination of C60 with SbCl5 enables chlorine migration and thus leads to the most favorable chlorination patterns that can differ from the room‐temperature ones. We report the isolation and characterization of several IPR chlorofullerenes of intermediate stoichiometry: C60Cl8, C60Cl10, C60Cl14, and C60Cl24, together with the non‐IPR 1805C60Cl24 and 1794C60Cl20, and a product of fullerene cage shrinkage, C58Cl20.