In Search of Fullerene‐Based Superacids: Synthesis, X‐ray Structure, and DFT Study of C₆₀(C₂F₅)₅H

Abstract

Simply super! The perfluoroalkylfullerene C(60)(C(2)F(5))(5) H is the first structurally characterized perfluoroalkylated fullerene-based acid and is also predicted to be the first gas-phase fullerene-based superacid.

Perfluoroalkylfullerenes

“…The only example of this approach was published in 2011 (T1#110). 103 A mixture of C 60 (C 2 F 5 ) 2,4 and C 60 (C 2 F 5 ) 1,3,5 H was prepared by the reaction of C 60 Cl 6 with LiC 2 F 5 at ca. −95 °C in toluene solution (note that LiC 2 F 5 is thermally unstable and has to be prepared at low temperature and used immediately).…”

“…The only unambiguous exception is the preparation of several C 2 F 5 derivatives of C 60 by nucleophilic substitution (T1#110). 103 The formation of TMFs during the carbon arc discharge synthesis of fullerenes is of historical interest but is not practical because yields are extremely low and because the product mixtures are extremely complex. The formation of mixed fullerene(F) n (R F ) m derivatives during fullerene fluorination reactions is also impractical because of extremely low yields.…”

Ion formation pathways of crown ether–fullerene conjugates in the gas phase

“…37,42 The analyte, on the other hand, may well show a considerable degree of acidity as observed for related compounds. [9][10][11][12][13] The behaviour of the crown ether adducts in ESI confirm the assumed acidity by the abundant formation of their deprotonated anions (see above).…”

“…The formation of these species is perfectly in line with the fact that C 60 HR compounds of this type are acidic. [9][10][11][12][13] Evidently deprotonation is more attractive than electrochemical reduction as alternative ion formation mechanism which is occasionally operative for other, non-acidic derivatised fullerenes. 3 Upon activation, the crown ether radical is released which identifies the fullerene as expected as the charge carrier ( Fig.…”

Reductive Hydrogenation of Cs‐C70(CF3)8 and C1‐C70(CF3)10

“…[8] Besides,arelatedC 60 (C 2 F 5 ) 5 Hm olecule with skew pentagonal pyramid addition pattern and superacidic properties has been recently synthesized via reaction of C 60 Cl 6 with C 2 F 5 Li. [9] Nevertheless, possible selectiveh ydrogenation of poly (trifluoromethyl)fullerenes has not been addressed yet.…”