Stable [60]fullerene carbocations

Avent, Anthony G.; Birkett, P. R.; Kroto, Harold W.; Taylor, Roger; Walton, D. R. M.

doi:10.1039/a806336b

Cited by 38 publications

(44 citation statements)

References 15 publications

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“…For example, previously no reaction was observed between mesitylene and C 60 Cl 6 . [8] However, the smaller size of fluorine reduces this problem and ortho substitution occurs here in reaction with toluene, biphenyl, diphenyl ether, and surprisingly, at the 1-position of naphthalene.…”

Section: Resultsmentioning

confidence: 92%

“…[6] This led to isolation and characterisation of compounds such as, C 60 Ar 5 Cl and C 60 Ph 5 H, [7,8] C 60 Ph 4 and C 60 Ph 2 , [9] a phenylated isoquinolino [3,4:1,2][60]fullerene, [10] benzo [b]furano[60]-and [70]fullerenes, [11] C 70 Ph 10 and C 70 Ph 8 , [12] C 70 Ph 9 OH, [13] and two [70]fullerendiol isomers, C 70 Ph 8 (OH) 2 . [14] The use of a fluorofullerene as an electrophile has been reported in one study only, involving the FeCl 3 -catalysed reaction of C 60 F 18 with benzene, which produced the triphenyl derivative ("triumphene") (1, Ar= Ph).…”

Section: Introductionmentioning

confidence: 97%

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Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Darwish

Avent

Abdul‐Sada

et al. 2004

Chemistry A European J

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The FeCl3-catalysed arylation of C60F18 gives tri-substituted compounds C60F15Ar3, where Ar=phenyl, 4-tolyl, 4-methoxyphenyl, 4-phenoxyphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-biphylenyl and 2-fluorenyl, together with some bis- and mono-substituted product. Bis-substitution was achieved with biphenylene and fluoranthene, and mono-substitution with biphenylene (2-position), pyrene (1-position), and naphthalene (1- and 2-positions); the tris-phenyl and tris-biphenylene derivatives are fluorescent. The 2-naphthyl substituent freely rotates at 328 K, whereas rotation of the 1-naphthyl substituent is prevented by interaction of the peri-hydrogen atom with fluorine. The 1-naphthyl derivative eliminates a molecule of HF during EI mass spectrometry, whilst the 2-naphthyl derivative eliminates HF and all fluorenes to give a naphthaleno[60]fullerene. The reaction rate is relatively unaffected by electron supply in the aryl rings, but no product was obtained with benzotrifluoride which defines the lower reactivity limit. The low discrimination between aromatics makes it possible to isolate derivatives having different aryl groups attached to the cage. Reactions occur mainly when the reagent solutions (or solutions in 1,2-dichlorobenzene) are evaporated to dryness. In most FeCl3-catalysed reactions, unreacted C60F18 was recovered, more if the less effective SnCl4 was used as a catalyst; use of AlCl3 resulted in polyarylation and degradation of the C60F18. The structure of C60F17(1-biphenylyl) was confirmed by single-crystal X-ray analysis. Reaction of C60F18 with perylene/FeCl3/o-dichlorobenzene gave red fluorescent "tagliatelli"-like threads (up to 1 cm long) of self-assembled pi-stacked tetrachloroperylene arising from chlorination by FeCl3.

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Section: Resultsmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 97%

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Darwish

Avent

Abdul‐Sada

et al. 2004

Chemistry A European J

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“…+ , formed by treating C 60 Ar 5 Cl (Ar = Ph or 4-FC 6 H 4 ) with AlCl 3 , to the more stable C s isomer (analogous to A). [16] Addition of AlCl 3 to 2 a led to heterolysis of the peroxo OÀO bond and formation of hemiketal fullerene derivatives. The reaction gave two regioisomers 3 and 4 (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

Preparation of [5,6]‐ and [6,6]‐Oxahomofullerene Derivatives and Their Interconversion by Lewis Acid Assisted Reactions of Fullerene Mixed Peroxides

Huang

Xiao

Wang

et al. 2005

Chemistry A European J

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[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results.

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“…This work presages the isolation of further RC 60 + cations and their use in chemical synthesis. Radical cations of hexachlorinated [60]fullerene 460 and spin-paired carbocations of pentaphenylated [60]fullerene 461 add to the growing dimension of cationic fullerene chemistry.…”

Section: +mentioning

confidence: 99%

Discrete Fulleride Anions and Fullerenium Cations

2000

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His research interests include reactive cation and superacid chemistry with inert carborane counterions, ionic liquids, bioinorganic chemistry, spin-coupling phenomena, fullerene chemistry, and new carbon-or porphyrin-based materials. He is a Sloan Fellow, a Dreyfus Teacher−Scholar Awardee, and a Guggenheim Fellow. Robert Bolskar received his B.S. degree in Chemistry from Carroll College in Waukesha, WI, in 1992. He earned his Ph.D. degree at the University of Southern California in Los Angeles under the direction of Christopher Reed in 1997, investigating the synthetic redox chemistry of fullerene anions and cations. In 1998 he moved to the University of California, Riverside, as Managing Research Associate. He is currently Senior Chemist at TDA Research in Wheat Ridge, CO. His research interests include the chemistry and physics of fullerene compounds, supramolecular chemistry, strongly oxidizing systems, and electrophilic cations.

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Stable [60]fullerene carbocations

Cited by 38 publications

References 15 publications

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Preparation of [5,6]‐ and [6,6]‐Oxahomofullerene Derivatives and Their Interconversion by Lewis Acid Assisted Reactions of Fullerene Mixed Peroxides

Discrete Fulleride Anions and Fullerenium Cations

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Stable [60]fullerene carbocations

Cited by 38 publications

References 15 publications

Electrophilic Aromatic Substitution by the Fluorofullerene C60F18

Electrophilic Aromatic Substitution by the Fluorofullerene C60F18

Preparation of [5,6]‐ and [6,6]‐Oxahomofullerene Derivatives and Their Interconversion by Lewis Acid Assisted Reactions of Fullerene Mixed Peroxides

Discrete Fulleride Anions and Fullerenium Cations

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Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈

Electrophilic Aromatic Substitution by the Fluorofullerene C₆₀F₁₈