Oxidations of Fullerenes

In contrast to the relative ease of reduction, oxidation of fullerenes requires more severe conditions [113, 114]. Not only does the resonance stabilization raise the level of the corresponding oxidation potential (1.26 V versus Fc/Fc ), but also the reversibility of the underlying redox process is affected [115]. 

In contrast to the relative ease of the preparation of fullerides, the oxidation of fullerenes is not straightforward. It has been determined that the ease of oxidation follows the pattern Qo < C70 < QsCQu) < C76 < Q4 < C Z ).85 Thus it was no surprise that the first isolated fullerene carbocation contains one of the bigger fullerenes, namely C76 it can be made according to ... 

The oxidation of fullerenes is much more difficult than their reduction because of the highly positive oxidation potentials (1.26 V relative to Fc/Fc+ for Ceo) [16]. Since the five HOMO orbitals of Ceo hf are degenerate and fully occupied, Ceo may be oxidized up to The formation of in which 7 electrons were... 

The oxidative electrochemistry of fullerenes is not as rich as the reductive. Most of the solvent/background electrolyte combinations studied to date have too limited a potential window for the oxidation of fullerenes to be observed. Oxidation of C o was first studied by Jehoulet et al. [58] who found that a solid C o film oxidizes totally irreversibly in acetonitrile. Dubois et al. [30] found a single totally irreversible oxidation at -f-1.30 V vs. ferrocene for both 50 tmd... 

One aspect that reflects the electronic configuration of fullerenes relates to the electrochemically induced reduction and oxidation processes in solution. In good agreement with the tlireefold degenerate LUMO, the redox chemistry of [60]fullerene, investigated primarily with cyclic voltammetry and Osteryoung square wave voltammetry, unravels six reversible, one-electron reduction steps with potentials that are equally separated from each other. The separation between any two successive reduction steps is -450 50 mV. The low reduction potential (only -0.44 V versus SCE) of the process, that corresponds to the generation of the rt-radical anion 131,109,110,111 and 1121, deserves special attention. 

Parallel to the shift that the reduction of higher fullerenes shows, oxidation of the latter is also made easier... 

Reduction of fullerenes to fullerides — Reversible electrochemical reduction of Ceo in anhydrous dimethylformamide/toluene mixtures at low temperatures leads to the air-sensitive coloured anions Qo" , ( = 1-6). The successive mid-point reduction potentials, 1/2, at -60°C are -0.82, -1.26, -1.82, -2.33, —2.89 and —3.34 V, respectively. Liquid NH3 solutions can also be used. " Ceo is thus a very strong oxidizing agent, its first reduction potential being at least 1 V more positive than those of polycyclic aromatic hydrocarbons. C70 can also be reversibly reduced and various ions up to... 

In 2000, it was proposed that the regioselectivity of the [3 + 2] cycloaddition of fullerenes could be modified under microwave irradiation. Under conventional heating, N-methylazomethine yhde and fullerene-(C7o) gave three different isomeric cycloadducts because of the low symmetry of C70 vs. Ceo. Using microwave irradiation and o-dichlorobenzene as a solvent, only two isomers were obtained, the major cycloadduct 114 being kinetically favored (Scheme 39) [75]. The same authors had previously reported the 1,3-dipolar cyclo addition of pyrazole nitrile oxides, generated in situ, to Geo under either conventional heating or microwave irradiation. The electrochemical characteristics of the cycloadduct obtained with this method made this product a candidate for photophysical apphcations [76]. 

Eguchi and Ohno have used silyl nitronate induced 1,3-dipolar cycloaddition for functionalization of fullerene C60 (Eq. 8.76).127a Nitrile oxides also undergo 1,3-dipolar cycloaddition... 

Fullerenes Cycloaddition reactions are very popular for functionalization of fullerenes. Such reactions of fullerenes are compiled and discussed in detail in Reference 253. During the last 10 to 15 years, several communications appeared concerning [3 + 2] cycloaddition of nitrile oxides to fullerene C60- Nitrile oxides, generated in the presence of C60, form products of 1,3-cycloaddition, fullerene isoxazolines, for example, 89. The products were isolated by gel permeation chromatography and appear by and 13 C NMR spectroscopy to be single isomers. Yields of purified products are ca 30%. On the basis of 13C NMR, structures with Cs symmetry are proposed. These products result from addition of the nitrile oxide across a 6,6 ring fusion (254). 

Similarly, other cycloadducts of nitrile oxides with C6o were synthesized. The cycloadducts were characterized by 13C NMR spectroscopy and high-resolution fast atom bombardment (FAB) mass spectrometry. It should be mentioned that X-ray structure determination of the 3-(9-anthryl)-4,5-dihydroisoxazole derivative of C6o, with CS2 included in the crystals, was achieved at 173 K (255). Cycloaddition of fullerene C60 with the stable 2-(phenylsulfonyl)benzonitrile oxide was also studied (256). Fullerene formed with 2-PhSC>2C6H4CNO 1 1 and 1 2 adducts. The IR, NMR, and mass spectra of the adducts were examined. Di(isopropoxy)phosphorylformonitrile oxide gives mono- and diadducts with C60 (257). Structures of the adducts were studied using a combination of high performance liquid chromatography (HPLC), semiempirical PM3 calculations, and the dipole moments. 

Many papers and patents are devoted to the use of nitrile oxides for the preparation of fullerene derivatives with practically attractive properties. 

Aulbach M, Ter Meer HU. Preparation of fullerene-nitrile oxide adducts, Ger. Pat. 4240042 1994. [Chem. Abstr. 1995 122 31507],... 

Balance equations, for a mixture, 24 669-671 Balances 26 227 analytical, 26 245 precision, 26 245 Balke process, 17 139 B-Alkyl-9-BBN derivatives, 13 658 B-Alkylcatecholboranes, free-radical oxidations of, 13 648 Ball and chain structures, fullerene, 12 252... 

Cationic species of fullerenes have long been considered to be difficult to prepare, based on the well-known resistance of C , toward oxidation. However, reliable methods are now available for the preparation of alkylated fullerene cations RC60+ and RC70+ as long-lived species, allowing their structures and properties to be investigated in detail. Precise evaluation of their thermodynamic stabilities revealed that these cations have stabilities comparable to the terf-butyl cation. 

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