Multiple, reversible chlorination of C60

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

“…Small amounts of the product were purified by HPLC (toluene eluent) to 99 % purity. The pure compound C s -C 60 Cl 6 is stable for at least three months as a solvent-free powder at 25 8C. The Raman, far-IR, and MALDI mass spectra of pure C s -C 60 Cl 6 are reported for the first time.…”

“…The pure compound C s -C 60 Cl 6 is stable for at least three months as a solvent-free powder at 25 8C. The Raman, far-IR, and MALDI mass spectra of pure C s -C 60 Cl 6 are reported for the first time. The Raman and far-IR spectra, the first reported for any C 60 Cl n chlorofullerene, were used to carry out a vibrational analysis of C s -C 60 Cl 6 at the DFT level of theory.…”

“…Dozens of C 60 derivatives containing from 2 to 48 fluorine atoms and, in many cases, other substituents as well have been extensively studied. [1,2] In addition, bromination of C 60 yielded the three single-composition/singleisomer products C s -C 60 Br 6 , C 2v -C 60 Br 8 , and T h -C 60 Br 24 , all of which have been structurally characterized. [3,4] As far as chloro [60]fullerenes are concerned, the situation is paradoxical.…”

“…Although chlorination was one of the first C 60 derivatizations reported in the literature, revealing the formation of C 60 Cl 6 [5] and putative C 60 Cl n compounds with up to 24 chlorine atoms s-bonded to the C 60 cage, [6,7] structurally-characterized compounds such as T h -C 60 Cl 24 , [8] C 1 -C 60 Cl 28 , [9] C 2 -C 60 Cl 30 , [9] and D 3d -C 60 Cl 30 [10] have only been reported in the past few months (the compound C 60 Cl 6 is believed to have the same structure as C s -C 60 Br 6 based on its 13 C NMR spectrum [5] ). Nevertheless, after nearly 15 years the compositional purity of C 60 Cl 6 , which has always been assumed to be high, [5,11,12] has never been satisfactorily demonstrated (i.e., none of the three previous reports of its synthesis properly established its purity [5,11,12] ). In fact, recent work by us [13] and others [14] suggests that it may be only about 75 % pure.…”

“…MALDI mass spectrometry was used for the first time to identify other components of the reaction mixtures. An improved synthetic procedure was developed for the synthesis of about 150 mg batches of chlorofullerenes containing 90 % C s -C 60 Cl 6 based on HPLC intensities. The optimum reaction time was decreased from several days to seven minutes.…”