The structure of C60Ph5Cl and C60Ph5H, formed via electrophilic aromatic substitution

Abstract

Reaction of c6&& with benzene/FeCI3 yields C60Ph5CI which is readily reduced t o C60Ph5H, the main product of reacting c 6 0 with BrJFeCIdbenzene; both compounds have been characterised by NMR spectroscopy.The sp2-hybridised carbon framework and the associated cage strain makes [60]fullerene a potent electrophile.1 [60]Fullerene appears to be more electrophilic than [70]fullerene, as indicated by the IH resonances in the NMR spectra of hydrogenated [60]fullerenes lying considerably downfield from those for hydrogenated [70]fullerenes2~3 and by the equilibrium constants for reaction of [a]and [70]-fullerenes with N,N-dime t hylaniline .4We showed previously that C60Ph12 was amongst the products obtained in electrophilic substitution of benzene by [60]fullerene in the presence of Br2/FeC13.5 Friedel-Crafts reaction of polychlorinated [60]fullerenes with benzene gave products containing up to 22 phenyl groups.6 We have now isolated some 10 products (some as yet uncharacterised) from the former reaction, find that the main product is CmPhSH, and that this is also formed by reacting CmCl6 (which we described recently)7 with benzene/FeC13 followed by reduction.CmPh5C1 was prepared by heating CmCl67 with benzene-FeCI3 for 20 min, cooling, washing the benzene layer with water, separating and drying (MgS04). The residue obtained after benzene removal was set aside to crystallise from carbon tetrachloride, and gave translucent orange crystals (68%). These crystals contain CC14 trapped in the lattice, for on heating to ca. 80 "C they become opaque, the loss of CC14 was also monitored by IR spectroscopy. The mass spectrum (Fig. 1, EI, heated DCI probe), the first obtained for a chlorinated fullerene, confirmed the molecular formula as CmPh5C1. The

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

“…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.…”

“…[7] Subsequent papers by others reported the use of C 60 Cl 6 to prepare organic derivatives of C 60 . [14][15][16] It is possible that chlorofullerenes could also be used to prepare new inorganic fullerene derivatives under mild conditions (a recent, related example involving a bromofullerene is the transformation of T h -C 60 Br 24 to kinetically-stable T h -C 60 F 24 at 25 8C [17] ). However, significant progress in the use of chlorofullerene synthons Abstract: Three previously reported procedures for the synthesis of pure C s -C 60 Cl 6 from C 60 and ICl dissolved in benzene or 1,2-dichlorobenzene were shown to actually yield complex mixtures of products that contain, at best, 54-80 % C s -C 60 Cl 6 based on HPLC integrated intensities.…”

Electrophilic Aromatic Substitution by the Fluorofullerene C60F18

“…[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).…”

Synthesis and Characterization of Pentaarylated [60]Fullerene Coordinated Complexes [(η2‐Ar5C60H)M(PPh3)2] (M = Pt, Pd) and an ab initio Study on Their Isomerism

“…[1,2] Later on, a more convenient one-pot method for preparation of Ar 5 C 60 H was discovered, involving treatment of C 60 with organocopper/magnesium reagents Ar 2 CuMgBr, followed by treatment of the reaction mixture with aqueous NH 4 Cl. [3,4] It is conceivable that the pentaarylated [60]fullerene derivatives Ar 5 C 60 H might form organometallic complexes with single, double, triple, and even multiple metal centers through their pentaarylated cyclopentadienyl rings and other sites of the C 60 core in a variety of coordination modes from η 1 to η 6 .…”

“…, which resemble those of the free ligands C 60 [8] and Ar 5 C 60 H (Ar ϭ Ph, [1] m-MeC 6 H 4 , [9] pMeC 6 H 4 [2] ).…”