1. New developments in the organic chemistry of fullerenes
- Author
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Bellavia-Lund, C., Hummelen, J.C., Keshavarz, K., Gonzalez, R., Wudl, F., Keshavarz-K., Majid, Molecular Energy Materials, and Stratingh Institute of Chemistry
- Subjects
chemistry.chemical_classification ,Fullerene ,010405 organic chemistry ,Thermal decomposition ,General Chemistry ,010402 general chemistry ,Condensed Matter Physics ,01 natural sciences ,Medicinal chemistry ,Cycloaddition ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Computational chemistry ,Yield (chemistry) ,ComputingMethodologies_DOCUMENTANDTEXTPROCESSING ,Surface modification ,General Materials Science ,Azide ,Selectivity ,GeneralLiterature_REFERENCE(e.g.,dictionaries,encyclopedias,glossaries) ,Alkyl - Abstract
Unlike the addition of a second equivalent of diazoalkane to C60, which does not show marked selectivity, the addition of azides to C60 shows chemo and regio selectivity [4]. Utilization of this unique selectivity, led us to the preparation of the first heterofullerene ‘C59N’ in bulk quantity [5, 6]. Herein we report on its synthesis and mechanism of formation. We also describe the application of this procedure for the formation of higher heterofullerene analogs, i.e. ‘C69N’ isomers [7] and introduce methodology that opens a viable route to the functionalization of azafullerenes [8]. The azafullerene (C59N)2 can be synthesized from C60 in three steps. The initial step in the formation of azafullerenes is the 1,3-dipolar cycloaddition of 2methoxyethoxymethyl azide (MEM-azide) [9]. Not unlike the addition of diazoalkane, the addition of an alkyl azide to C60 occurs across the [6,6] bond. At room temperature, the initially formed triazoline can be isolated in 35-40% yield. Thermolysis of the triazoline, followed by concomitant loss of nitrogen, gives rise to azafulleroids and fulleroaziridines. Fulleroaziridines and azafulleroids can also be obtained directly from C60 at higher reaction temperatures (160-180°C).
- Published
- 1997