Chlorination-Promoted Cage Transformation of IPR C 92 Discovered via Trifluoromethylation under Formation of Non-classical C 92 (NC)(CF 3 ) 22 .

High-temperature trifluoromethylation of isolated-pentagon-rule (IPR) fullerene C ₉₂ chlorination products followed by HPLC separation of C ₉₂ (CF ₃ ) _n derivatives resulted in the isolation and X-ray structural characterization of IPR C ₉₂ (38)(CF ₃ ) ₁₈ and non-classical C ₉₂ (NC)(CF ₃ ) ₂₂ . The formation of C ₉₂ (38)(CF ₃ ) ₁₈ as the highest CF ₃ derivative of the known isomer C ₉₂ (38) can be expected. The formation of C ₉₂ (NC)(CF ₃ ) ₂₂ was interpreted as chlorination-promoted cage transformation of C ₉₂ (38) followed by trifluoromethylation of non-classical C ₉₂ (NC) chloride. Noticeably, C ₉₂ (NC)(CF ₃ ) ₂₂ shows the highest degree of trifluoromethylation among all known CF ₃ derivatives of fullerenes. The addition patterns of C ₉₂ (38)(CF ₃ ) ₁₈ and C ₉₂ (NC)(CF ₃ ) ₂₂ are discussed and compared to the chlorination patterns of C ₉₂ (38)Cl _n compounds.
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)