Fullerene chemistry

The scope of tire following article is to survey the physical and chemical properties of tire tliird modification of carbon, namely [60]fullerene and its higher analogues. The entluisiasm tliat was triggered by tliese spherical carbon allotropes resulted in an epidemic-like number of publications in tire early to mid-1990s. In more recent years tire field of fullerene chemistry is, however, dominated by tire organic functionalization of tire highly reactive fullerene... 

Prato M 1997 [60]fullerene chemistry for materials science applications J. Mater. Chem. 7 1097-109... 

DIederIch F and Thilgen C 1996 Covalent fullerene chemistry Sc/e/ ce271 317-23... 

Jensen A W, Wilson S R and Schuster D I 1996 Biological applications of fuiierenes—a review Bioorg. Med. Chem. 4 767-79 Martii n N, Sanchez L, lllescas B and Perez I 1998 Cgg-based electroactive organofullerenes Chem. Rev. 98 2527 Prato M 1997 [60]fullerene chemistry for materials science applications J. Mater. Chem. 7 1097-109... 

The field of fullerene chemistry expanded in an unexpected direction in 1991 when Sumio lijima of the NEC Fundamental Research Laboratories in Japan discovered fibrous carbon clusters in one of his fullerene preparations This led within a short time to substances of the type portrayed in Figure 11 7 called single-walled nanotubes The best way to think about this material IS as a stretched fullerene Take a molecule of Ceo cut it in half and place a cylindrical tube of fused six membered carbon rings between the two halves... 

Fullerene chemistry leading to novel fullerene-like molecules with new chemical groups that are radially attached has become a very active research field, largely because of the uniqueness of the Cgo molecule and the variety of chemical reactions that appear to be possible [30, 31]. Many new fullerene-based molecules have already been synthesized and characterized chemically,... 

Heteroatom fullerene-type clusters — The possibility of incorporation of hetero atoms into C clusters has excited the attention of both theoreticians and experimentalists since the earliest days of fullerene chemistry, particularly in view of the known stability and ubiquity of organic heterocycles. The structural relationship between Ceo and /3-rhombohedral boron has already been alluded to (p. 142). 

Averdung J., Torres-Garcia G., Luftmann H., Schlachter L, Mattay J. Progress in Fullerene Chemistry From Exohedral Functionalization to HeterofuUerenes. 

Ceo and higher fullerenes are distinguished from other allotropes of carbon, diamond and graphite, in that they exist as discrete molecules. The spherical or ellipsoidal nature of the monotropes opens up the possibility of intriguing new areas of chemistry. Here we are only interested in the hydrogen (or muonium) adducts, although this study has important implications to the very vigorous and extensive research in fullerene chemistry. 

Hammond, G. S., and Kuck, V. J., Eds. (1992). Fullerenes. American Chemical Society, Washington, DC. This is ACS Symposium Series No. 481, and it presents a collection of symposium papers on fullerene chemistry. 

Kroto, H. W., Fisher, J. E., and Cox, D. E. (1993). The Fullerenes. Pergamon Press, New York. A reprint collection with articles on most phases of fullerene chemistry. 

Aspects of Covalent Fullerene Chemistry Regioselective Multiple Functionalization, Optically Active Carbon Allotropes, and Electroluminescent Devices (LEDs)... 

F. Diederich, M. Gomez-Lopez, Supramolecular Fullerene Chemistry , Chem. Soc Rev. 1999, 28, 263-277. 

F. Diederich, C. Thilgen, Covalent Fullerene Chemistry , Science 1996, 271, 317-323. 

F. Diederich, R. Kessinger, Templated Regioselective and Stereoselective Synthesis in Fullerene Chemistry , Acc Chem Res. 1999, 32, 537-545. 

Hirsch, A. Brettreich, M. Fullerenes Chemistry and Reactions Wiley-VCH Weinheim, 2005 chapter 3. 

Dugan LL, Lovett E, Cuddihy S, Ma B-W, Lin T-S, Choi DW (2000) Carboxyfullerenes as neuroprotective antioxidants. In Kadish KM, Ruoff RS (eds.) Fullerenes Chemistry, Physics, and Technology. Wiley, New York, pp. 467 479. 

Martin N (2006) New challenges in fullerene chemistry. Chem. Commun. 2093-2104. 

Hirsch A, Lamparth I, Karfunkel HR (1994) Fullerene chemistry in three dimensions isolation of seven regioisomeric bisadducts and chiral trisadducts from C60 and bis(ethoxycarbonyl)methyl ene. Angew. Chem. Int. Ed. Engl. 33 437 138. 

Hirsch A, Brettreich M (2005) Fullerenes - Chemistry and Reactions. Wiley-VCH Verlag, Weinheim. 

Wilson SR (2000) Fullerenes chemistry, physics and technology. Wiley, New York. 

Taylor R (1999) Lecture Notes on Fullerene Chemistry. A Handbook for Chemists. Imperial College Press, London. 

Wilson SR (2000) Biological aspects of fullerenes. Chapter 10 in Fullerenes Chemistry, Physics and Technology, edited by Kadish K.M. and Ruoff, R.S. Wiley-Interscience, New York. 

In textbooks of fullerene chemistry, hydrogenation is the simplest reaction and fullerene hydrides are the simplest derivatives of fullerenes. Hydrogenation can be conducted under pressure and elevated temperatures. Heating at 400°C and 80 atm H yields red solid, [40]. Up to 48 H atoms can be added to under more forcing conditions. Catalytic hydrogenation at 280°C and 160 atm with use of Ru/C catalyst produce hydrofulerenes up to [41]. Hydrogenation is quite... 

The 1,3-dipolar addition reaction of fullerene with diazo compounds is one of the most studied reactions in the early stage of the research on fullerene chemistry [7]. The reaction in solution first affords rather labile fulleropyrazoline derivative 26, which is readily converted to the so-called 5,6-open (a bond originally shared by five- and six-membered rings cleaved) fulleroid (27) or 6,6-closed (a bond shared by two six-membered rings remaining closed) methanofullerene derivatives (28) by heat (e.g., refluxing in toluene) or photoirradiation (UV light), respectively (Scheme 11) [7a]. 

Reductive transformations of fullerenes have not only been carried out to prepare fulleride salts. The fulleride ions themselves are reactive species and easily undergo subsequent reactions, for example, with electrophiles. Therefore, the anions provide a valuable synthetic potential for fullerene chemistry. 

In cycloaddition reactions the [6,6] double bonds of Cjq exhibit a dienophilic character. A large variety of cycloadditions have carried out with Cjq and the complete characterization of the products, mainly monoadducts, has greatly increased our knowledge of fullerene chemistry. These chemical transformations also provide a powerful tool for the functionalization of the fullerene sphere. Almost any functional group can be covalently linked to Cjq by the cycloaddition of suitable addends. Some types of cycloadducts exhibit a remarkable stability for example, they can be thermally treated up to 400 °C without decomposition. This is an important requirement for further side-chain chemistry as well as for possible applications of the new fullerene derivatives, which may be of interest due to their biological activity or as new materials. 

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