Trifluoromethyl derivatives of pentagon-fused C60: 1809C60(CF3)n (n = 10, 12, 14, 16)

Tamm, Nadezhda B.; Markov, Vitaliy Yu.; Troyanov, Sergey I.

doi:10.1039/d1dt00493j

Cited by 7 publications

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“…For example, high-temperature trifluoromethylation of non-IPR chlorides affords CF 3 derivatives with the same non-IPR cages, whereas the addition patterns may differ substantially. In this way, CF 3 derivatives of non-IPR C 60 , 1809 C 60 (CF 3 ) 10–16 , 1810 C 60 (CF 3 ) 14 , 1807 C 60 (CF 3 ) 12 , and nonclassical C 60 ( NC )(CF 3 ) 15 F have been obtained. , …”

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Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C₆₀: Non-IPR ¹⁸⁰⁹C₆₀Cl₈, ¹⁸⁰⁶C₆₀(CF₃)₁₄, and Nonclassical C₆₀(NC)Cl₁₄

et al. 2022

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High-temperature chlorination of conventional IPR C 60 can produce chloro derivatives of non-IPR C 60 by skeletal transformations via Stone−Wales rearrangements (SWRs) of the carbon cage. We report the synthesis and structure elucidation of non-IPR 1809 C 60 Cl 8 and nonclassical C 60 (NC)Cl 14 . The present isolation of 1809 C 60 Cl 8 hints at the possibility that the same product in the previously reported chlorine-doped arc-discharge synthesis could have, likewise, resulted from the initially formed IPR C 60 . C 60 (NC)Cl 14 is the first chloride containing a nonclassical carbon cage with one heptagon and 13 pentagons known previously only in a CF 3 derivative. Additionally, trifluoromethylation of non-IPR chlorides revealed the formation of 1806 C 60 (CF 3 ) 14 with a new non-IPR carbon cage and unusual trifluoromethylation pattern. Thereby, the number of different, structurally confirmed non-IPR carbon cages of C 60 now reaches eight.A conventional Kraẗschemer−Huffman arc-discharge process produces fullerene soot which contains extractable fullerenes obeying the Isolated-Pentagon Rule (IPR). 1 Non-IPR fullerenes do not form because of their lower thermodynamic stability. 2 Therefore, the most abundant fullerene, C 60 , is present in the fullerene soot as the only IPR isomer I h -C 60 (or 1812 C 60 according to the spiral algorithm 1b ), whereas 1811 other topologically possible isomeric C 60 cages contain fused pentagons. 1b Generally, exohedral addition rarely changes the carbon cage connectivity. Consequently, the most investigated derivatives of C 60 possess the same IPR connectivity of the carbon cages. 3 Several derivatives of non-IPR fullerenes, including C 60 , were isolated using two different methods. An arc-discharge fullerene synthesis in the presence of chlorine-containing additives (Cl 2 , CCl 4 ) followed by chromatographic separation of the obtained fullerene mixture resulted in the isolation of two non-IPR chlorofullerenes, 1809 C 60 Cl 8 and 1804 C 60 Cl 12 . 4 The authors believe that the addition of chlorine provides the stabilization of non-IPR C 60 cages which are present in hightemperature plasma.The second method consists of high-temperature (400−440 °C) chlorination of IPR 1812 C 60 with SbCl 5 . 5 Under these conditions, cage transformations occur which proceed via Stone−Wales rearrangements (SWRs), i.e., rotations of one or several C−C bonds by 90°and formation of pentagon− pentagon fusions. 6 It was shown by theoretical calculations that the formation of chlorinated pentagon−pentagon junctions is thermodynamically strongly favorable. 5a,7

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Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C₆₀: Non-IPR ¹⁸⁰⁹C₆₀Cl₈, ¹⁸⁰⁶C₆₀(CF₃)₁₄, and Nonclassical C₆₀(NC)Cl₁₄

et al. 2022

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“…The molecule of C 2 v - 1810 C 60 Cl 24 isolated in this study as a solvate with toluene is very similar to the molecules in the crystal structure with a mixed toluene/ o -dichlorobenzene solvate and in the solvent-free cocrystals with D 2 d - 1805 C 60 Cl 24 (Figure ). It is remarkable that all three structure determinations revealed the C 60 Cl 24 molecules possessing “Stone–Wales (SW) crosses” on both poles, as schematically shown by dashed lines in the top view in Figure . This feature could be interpreted as the presence of a 1805 C 60 cage instead of 1810 C 60 but the difference in the occupation of the crosses’ components allowed us to exclude this possibility.…”

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“…It was reported recently that chloro derivatives of non-IPR C 60 are formed upon high-temperature (400–440 °C) chlorination of IPR 1812 C 60 with SbCl 5 . The formation of non-IPR chlorofullerenes, i.e., the changes of the carbon cage connectivity, proceeds via Stone–Wales rearrangements (SWRs), which include rotations of C–C bonds by 90° .…”

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“…High-temperature trifluoromethylation of the chlorination products results in the formation of CF 3 derivatives without changing the carbon cage connectivities of the initial non-IPR chlorides. Several isolated and structurally characterized CF 3 derivatives of non-IPR C 60 include 1809 C 60 (CF 3 ) 10–16 , 1807 C 60 (CF 3 ) 12 , and nonclassical C 60 ( NC )(CF 3 ) 15 F containing a heptagon in the carbon cage …”

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“…In another experiment, part of the chlorination product was trifluoromethylated with gaseous CF 3 I in a quartz ampule at 450 °C in a gradient furnace for 3 h as reported previously. , Caution! The pressure of CF 3 I reaches ca.…”

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Chloro- and Trifluoromethyl Derivatives of a Pentagon-Fused C₆₀: ¹⁸¹⁰C₆₀Cl₂₄, ¹⁸¹⁰C₆₀Cl₂₀, and ¹⁸¹⁰C₆₀(CF₃)₁₄

et al. 2021

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The carbon cage of I h -C60, obeying the isolated-pentagon rule (IPR), can be transformed to the non-IPR D 2h -1810C60 cage via two successive Stone–Wales rearrangements in the course of high-temperature chlorination of C60 with SbCl5. Two chloro derivatives, C 2v -1810C60Cl24 and C 2v -1810C60Cl20, have been isolated by high-performance liquid chromatography (HPLC). High-temperature trifluoromethylation of the chlorination products with CF3I, followed by HPLC separation, afforded a non-IPR CF3 derivative, C s -1810C60(CF3)14. Structural elucidation of the isolated compounds revealed that all eight sites of pentagon–pentagon fusions on the carbon cage are preferentially occupied by Cl atoms or CF3 groups. According to density functional theory calculations, chloro and CF3 derivatives of 1810C60 are more stable than the isomeric derivatives of 1809C60 or IPR 1812C60, possessing respectively four or no sites of pentagon fusion in their carbon cages.

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Consecutive Trifluoromethylation of C₈₈(7) Fullerene: A Theoretical Study

Xu,

Liu,

2024

ChemistrySelect

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The trifluoromethylation of C88(7) fullerene has been systematically studied using an energy‐controlled consecutive CF3 addition approach. The thermodynamically favored C88(7)(CF3)2n isomers with 2n = 2–20 were predicted at the DFT B3LYP‐D3BJ/6–311G* level of theory for the first time, in harmony with the two experimentally characterized isomers C88(7)(CF3)12/16. It was found that these stable isomers are formed mainly by 1,4‐additions of CF3 groups, and meanwhile, there are a few stable isomers with isolated CF3 groups for 2n ≤ 12, with ortho addition for 2n > 12, and with triple‐hexagon‐junction addition for the highest degree of trifluoromethylation (2n ≥ 18). The addition patterns of CF3 groups were discussed in terms of the local structural motif of the pristine cage and the formation of stabilizing substructures of local aromaticity. The possible trifluoromethylation pathways of C88(7) were proposed on the basis of the relative Gibbs free energies. The results show that almost all the intermediate isomers for the thermodynamically most stable isomers of C88(7)(CF3)2n possess low relative Gibbs free energies (below 14 kJ·mol−1). Moreover, the hardness, chemical potential, electrophilicity index, electron affinity, HOMO and LUMO energies, and HOMO–LUMO gaps of the thermodynamically most stable C88(7)(CF3)2n isomers were also calculated.

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Trifluoromethyl derivatives of pentagon-fused C₆₀: ¹⁸⁰⁹C₆₀(CF₃)_n (n = 10, 12, 14, 16)

Abstract: The structural chemistry of trifluoromethyl derivatives of non-IPR 1809C60 is discussed and compared with related chloro derivatives for the first time.

Cited by 7 publications

References 21 publications

Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C₆₀: Non-IPR ¹⁸⁰⁹C₆₀Cl₈, ¹⁸⁰⁶C₆₀(CF₃)₁₄, and Nonclassical C₆₀(NC)Cl₁₄

Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C₆₀: Non-IPR ¹⁸⁰⁹C₆₀Cl₈, ¹⁸⁰⁶C₆₀(CF₃)₁₄, and Nonclassical C₆₀(NC)Cl₁₄

Chloro- and Trifluoromethyl Derivatives of a Pentagon-Fused C₆₀: ¹⁸¹⁰C₆₀Cl₂₄, ¹⁸¹⁰C₆₀Cl₂₀, and ¹⁸¹⁰C₆₀(CF₃)₁₄

Consecutive Trifluoromethylation of C₈₈(7) Fullerene: A Theoretical Study

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Trifluoromethyl derivatives of pentagon-fused C60: 1809C60(CF3)n (n = 10, 12, 14, 16)

Abstract: The structural chemistry of trifluoromethyl derivatives of non-IPR 1809C60 is discussed and compared with related chloro derivatives for the first time.

Cited by 7 publications

References 21 publications

Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C60: Non-IPR 1809C60Cl8, 1806C60(CF3)14, and Nonclassical C60(NC)Cl14

Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C60: Non-IPR 1809C60Cl8, 1806C60(CF3)14, and Nonclassical C60(NC)Cl14

Chloro- and Trifluoromethyl Derivatives of a Pentagon-Fused C60: 1810C60Cl24, 1810C60Cl20, and 1810C60(CF3)14

Consecutive Trifluoromethylation of C88(7) Fullerene: A Theoretical Study

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Trifluoromethyl derivatives of pentagon-fused C₆₀: ¹⁸⁰⁹C₆₀(CF₃)_n (n = 10, 12, 14, 16)

Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C₆₀: Non-IPR ¹⁸⁰⁹C₆₀Cl₈, ¹⁸⁰⁶C₆₀(CF₃)₁₄, and Nonclassical C₆₀(NC)Cl₁₄

Fused-Pentagon Carbon Cages in Chloro and Trifluoromethyl Derivatives of C₆₀: Non-IPR ¹⁸⁰⁹C₆₀Cl₈, ¹⁸⁰⁶C₆₀(CF₃)₁₄, and Nonclassical C₆₀(NC)Cl₁₄

Chloro- and Trifluoromethyl Derivatives of a Pentagon-Fused C₆₀: ¹⁸¹⁰C₆₀Cl₂₄, ¹⁸¹⁰C₆₀Cl₂₀, and ¹⁸¹⁰C₆₀(CF₃)₁₄

Consecutive Trifluoromethylation of C₈₈(7) Fullerene: A Theoretical Study