Evaluation of an Intramolecular Approach for the Synthesis of the Elusive C₅₈N₂ Heterofullerene Family

Abstract

A new approach towards the synthesis of the elusive heterofullerene C 58 N 2 is presented. The synthetic strategy is based on the intramolecular 1,3-dipolar cycloaddition of a spacerlinked azide to a monoazaheterofullerene (C 59 N) core. Since this cycloaddition can theoretically result in 16 different isomeric products, the design of the spacer moiety was based on extensive molecular modelling. Two fundamental synthetic routes towards suitably functionalized C 59 N derivatives were designed and carried out. Subsequent one-pot experiments, each making use of the same conditions as had previously

Synthesis of an Azahomoazafullerene C59N(NH)R and Gas‐Phase Formation of the Diazafullerene C58N2

“…The signal observed in this study is most likely due to the isomer with an NN moiety at the 6,6‐junction. Hirsch and co‐workers18 studied the preparation of C 58 N 2 through the intramolecular addition of an azide to the monoazafullerene C 59 NR and observed signals due to a mixture of C 59 N and C 58 N 2 ; the latter species accounted for up to 20 % of the mixture according to FAB mass spectra 18b. In contrast to the synthetic method described herein, the method described by Hirsch and co‐workers is designed to form a diazafullerene isomer with the two nitrogen atoms well apart from one another.…”

Progress in the Synthesis and Reaction of Azafullerene

“…Hirsch 等 [42,52] 2008 年 Hirsch 等 [53] 提出一种新的合成双氮杂富勒 烯的构想(Scheme 25). 合成策略是在氮杂富勒烯上引 入一个含有叠氮基团的长链, 之后进行分子内的 1,3-偶 极环加成反应, 根据 Wudl 合成氮杂 [60]富勒烯的方 法 [11] 再次引入一个氮原子, 从而实现双氮杂富勒烯 C 58 N 2 的合成.…”

On Stability, Chirality Measures, and Theoretical VCD Spectra of the Chiral C58X2 Fullerenes (X = N, B)

“…11, 12 Now, up to 20% of C 58 N 2 can be obtained by cycloaddition of a spacerlinked azide to the C 59 N core. 12 It has been shown that boron is more easily incorporated into carbon clusters and fullerenes than silicon 13 and that the predicted C 58 BN molecules 14,15 have been formed after laser ablation of C 2 BNÀgraphite. 16 In 1997, the C 2nÀ1 Si fullerenes were observed by Fye and Jarrold, 17 and the C 2nÀ2 Si 2 ones by Pellarin et al 18 In 1999, Ohtsuki et al detected formation of C 59 As and C 59 Ge by using radiochemical and radiochromatographic techniques.…”