Halogen and Interhalogen Reactions with [60]Fullerene: Preparation and Characterization of C₆₀C₂₄and C₆₀C₁₈F₁₄

Seven‐Minute Synthesis of Pure Cs‐C60Cl6 from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C60Cl6

“…The reported purity and yield of C 60 Cl 6 prepared by using the three reported syntheses that we have repeated were based on elemental analysis and IR and/or 13 C NMR spectroscopy. [5,12,20] However, elemental analysis only gives the average composition of a sample, IR spectroscopy is probably not sensitive enough to detect, for example, 10 % C 60 Cl 12 in a sample of C 60 Cl 6 , and 13 C NMR spectra of natural abundance, low-symmetry fullerene derivatives generally have such low signal-to-noise ratios that their value as an analytical tool is severely limited.…”

“…The need for a new synthesis: Since 1994, synthetic chemists who have used C 60 Cl 6 as a synthon [11,15,20,26] have assumed that the original procedure for its synthesis [5] provided a quantitative yield of pure material. The fact that this assumption went unchallenged for so long is probably due to the fact that chlorofullerene samples are particularly difficult to analyze.…”

“…Identical conditions but a longer reaction time, 5 d, led to the isolation of sample 2. [20] Sample 3 was obtained by mixing a filtered saturated solution of C 60 (13.5 mg, 0.0188 mmol) in 1,2-dichlorobenzene (0.5 mL) with ICl (20 mg, 6 mL, 0.12 mmol). [12] After 7 d, the red precipitate that had formed was separated from the supernatant by decantation, washed with benzene, and dried under vacuum.…”

“…Samples 1, 2, and 3 were prepared under the same conditions reported in refs. [5], [20], and [12], respectively; see Table 1 FAB [20] and MALDI [18,29] methods of ionization resulted in substantial fragmentation (i.e., loss of many chlorine atoms) when the substrates were chlorofullerenes with more than 24 chlorine atoms. Chlorofullerenes with low chlorine content, such as C 60 Cl 6 , were found to undergo complete C-Cl fragmentation under MALDI conditions to produce only chlorine-free ions such as C 60 + .…”

Synthesis and Structures of Fullerene Bromides and Chlorides

“…In another synthetic study, the product of UV irradiation of a solution of [60]-fullerene in chlorine-saturated carbon tetrachloride was suggested to be C 60 Cl 24 on the basis of fast-atom bombardment (FAB) mass spectrometric data. [23] Chlorination of C 60 with ICl or ICl 3 carried out in 1,2-dichlorobenezene seems to yield chlorofullerenes with compositions varying between C 60 Cl 6 and C 60 Cl 26 . [19] Treatment of C 60 with liquid chlorine under UV irradiation at room temperature gave a mixture of chlorofullerenes with compositions ranging from C 60 Cl 12 to C 60 Cl 32 according to MALDI-TOF mass spectrometry.…”