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Rsc Cc C3cc46247a 3..5 ChemComm View Article Online COMMUNICATION View Journal | View Issue An effective retro-cycloaddition of M3N@C80 Cite this: Chem. Commun., 2013, (M = Sc, Lu, Ho) metallofulleropyrrolidines† 49, 10489 Bo Wu,a Taishan Wang,a Zhuxia Zhang,a Yongqiang Feng,a Lihua Gan,b Li Jianga Received 15th August 2013, and Chunru Wang*a Accepted 17th September 2013 DOI: 10.1039/c3cc46247a www.rsc.org/chemcomm Sc3N@C80 fulleropyrrolidines are typical metallofullerene deriva- Echegoyen et al. proposed the isolation of metallofullerenes by an 16 tives which were generated by the reaction of Sc3N@C80 with electrochemical method. In this communication, we report N-trityloxazolidinone. Here we report an effective retro-reaction of a reversible cycloaddition reaction for TNT metallofullerenes, Sc3N@C80 fulleropyrrolidine by using 3-chloroperoxybenzoic acid which is considered to be a promising separation technique for to give pristine Sc3N@C80 in a high yield. This technique is metallofullerenes. expected to be used for separating metallofullerenes (M3N@C80) It is well known that the 1,3-dipolar cycloaddition reaction from hollow fullerenes without HPLC. between (metallo)fullerenes and azomethine ylides (Prato reac- tion) is widely used to prepare various (metallo)fulleropyr- Endohedral metallofullerenes (EMFs) are novel nanomaterials rolidines.17–19 Moreover, the retro-cycloaddition reactions of with stable nesting structures and unique electronic proper- fulleropyrrolidines and metallofulleropyrrolidines are also of ties.1–4 In this family, tri-metallic nitride template (TNT) cluster- great concern as the cycloaddition reversibility is related to 5–7 21 fullerenes, such as Sc3N@C80,Gd3N@C80,andLu3N@C80,have their yield optimization and recycling of metallofullerenes. attracted special attention due to their stable structures and high However, so far the reported retro-cycloaddition results have yields of production, and have found wide applications in medical always been achieved under special experimental conditions science,8 electronics,9 photochemistry,10 and materials science.11 such as metal-catalyzation,21 electrochemical redox,22 and micro The arc-discharging method is usually employed to produce wave elimination.23 In this report, we present a convenient and the TNT clusterfullerenes, which are always accompanied with efficient way to realize the retro-cycloaddition of M3N@C80 (M = 12 Published on 17 September 2013. Downloaded by Institute of Chemistry, CAS 06/12/2013 02:30:00. hollow fullerenes (C60,C70, etc.) and other metallofullerenes. Sc, Ho, Lu) metallofulleropyrrolidines using 3-chloroperoxy- Therefore, to separate and purify TNT clusterfullerenes in a benzoic acid (MCPBA) under moderate conditions. convenient way remains a big challenge in their application. In As shown in Fig. 1, Sc3N@C80 fulleropyrrolidine was synthe- 20 the past few decades, besides the expensive laboratory-used high- sized as reported previously. Briefly, Sc3N@C80 was heated performance liquid chromatography (HPLC) method, several with N-ethylglycine and paraformaldehyde at 120 1Cin non-HPLC approaches have been explored to isolate TNT cluster- o-dichlorobenzene (o-DCB) to give a metallofulleropyrrolidine 13 14 fullerenes. For example, Stevenson et al. adopted the cyclo- in a yield of 50%. C60 and C70 fulleropyrrolidines were also pentadiene (CPD) immobilized Merrifield resin as a reactive prepared for comparison. HPLC was employed to analyse the support for hollow fullerenes in a flash chromatographic column yields of products. Typically, these (metallo)fulleropyrrolidines to separate TNT clusterfullerenes from empty fullerenes. Soon were easily isolated by silica column chromatography. after that, they developed another non-chromatographic method named ‘‘Stir and Filter Approach’’ (SAFA)15 to purify metallofuller- enes by using cyclopentadienyl and amino functionalized silica. a Key Laboratory of Molecular Nanostructure and Nanotechnology, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China. E-mail: [email protected]; Fax: +86-10-62652120; Tel: +86-10-62652120 b School of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China † Electronic supplementary information (ESI) available: Experimental details, HPLC chromatograms, MALDI-TOF spectra and theoretical calculations. See DOI: 10.1039/c3cc46247a Fig. 1 Prato reaction and retro-cycloaddition of Sc3N@Ih-C80. This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 10489--10491 10489 View Article Online Communication ChemComm Fig. 2 HPLC profiles of the retro-cycloaddition of Sc3N@C80 fulleropyrrolidine for different reaction times. HPLC conditions: a 10 Â 250 mm Buckyprep column, 12 mL minÀ1 flow rate with toluene. Fig. 3 HPLC profiles of the retro-cycloadditions of Ho N@C and Lu N@C Table 1 The retro-cycloaddition of Sc N@C fulleropyrrolidine in the presence 3 80 3 80 3 80 fulleropyrrolidines. Black lines represent the metallofulleropyrrolidine reactants, of MCPBA at 40 1C for different reaction times and red lines denote the recovered TNT clusterfullerenes. Recovered Residual Sc3N@C80 a a Time (min) Sc3N@Ih-C80 (%) fulleropyrrolidine (%) derivatives, as the retro-reaction of [5,6] and [6,6] monoadducts 20 54.9 39.9 of Ho N@C took 30 and 15 minutes, respectively, to completely 25 82.6 15.1 3 80 30 86.1 0.3 convert into the pristine Ho3N@C80. Obviously, the retro- 40 68.1 0.0 cycloaddition of M3N@C80 (M = Sc, Ho, Lu) metallofulleropyr- 60 49.4 0.0 rolidines using MCPBA can be extended to be a universal a Determined by peak areas of HPLC profiles. technique for TNT clusterfullerenes. However, for hollow fullerenes C60 and C70, no retro-reaction of their corresponding fulleropyrrolidines was observed under The retro-reaction of Sc3N@C80 fulleropyrrolidine was similar experimental conditions (see ESI†). Instead, C60 and C70 achieved by adding MCPBA at 40 1C under stirring in o-DCB. pyrrolidine-N-oxides were produced using MCPBA as reported As shown in Fig. 2 and listed in Table 1, it was observed that in previous literature.24 In our experiments, as shown in Fig. S3 Sc3N@C80 fulleropyrrolidine was recovered to Sc3N@Ih-C80 and S4 (ESI†), the nitrogen oxides of C60 and C70 fullero- Published on 17 September 2013. Downloaded by Institute of Chemistry, CAS 06/12/2013 02:30:00. quickly, and after 30 minutes, the recovered Sc3N@Ih-C80 pyrrolidines were detected by MALDI-TOF mass spectroscopy reached a maximum yield of 86.11%. Further prolonging the and HPLC. However, the nitrogen oxide of Sc3N@C80 fullero- reaction time would lead to a significant loss of Sc3N@Ih-C80 pyrrolidine was not detected but obtained the parent Sc3N@Ih-C80. due to the oxidation of metallofullerenes. In comparison, a This phenomenon may be attributed to the unstable nitrogen oxide 21 previously reported retro-cycloaddition technique for Sc3N@C80 of Sc3N@C80 fulleropyrrolidine. Theoretical calculations were then fulleropyrrolidine requires it to be refluxed in o-DCB solution with employed to analyze the reason why the Prato products of hollow maleic anhydride and copper triflate, and required a reaction time fullerenes and TNT clusterfullerenes show different behaviors in of as long as 8–18 hours. Therefore, the current retro-reaction of the retro-cycloaddition. Ab initio calculations of the partial natural Sc3N@C80 fulleropyrrolidine is a fast and convenient process, bond orbital (NBO) charge distributions of three Prato derivatives which would significantly enhance its utility in the chemistry of reveal that the nitrogen atom of pyrrolidines has the most metallofullerenes. negative charge at ca. À0.5 eV in each molecule (see Fig. S6, The current retro-reaction technique is not only used for ESI†). Therefore, in the retro-reactions the peroxide in MCPBA Sc3N@C80 fulleropyrrolidine, but also for other TNT cluster- will attack the N atom of pyrrolidines to form a nitrogen oxide fullerene derivatives, such as Ho3N@C80 and Lu3N@C80 Prato group in the (metallo)fulleropyrrolidines. And also, the reason for products. M3N@C80 (M = Ho, Lu) metallofulleropyrrolidines the instability of nitrogen oxide of Sc3N@C80 fulleropyrrolidine were prepared and purified by a similar procedure to that of needs further theoretical calculations. Sc3N@C80 fulleropyrrolidine. In their retro-cycloaddition reac- The different behaviors of C60 fulleropyrrolidine, C70 fullero- tions, after adding MCPBA into the o-DCB solutions of M3N@C80 pyrrolidine, and TNT metallofulleropyrrolidines for this type of (M = Ho, Lu) metallofulleropyrrolidines at 40 1C, the pristine retro-cycloaddition are expected to lead to the development of a Ho3N@C80 and Lu3N@C80 were also successfully obtained, as new technique for separating TNT clusterfullerenes without the shown in Fig. 3. Fascinatingly, the retro-reaction time of metallo- use of the expensive HPLC method. For the sake of simplicity, fulleropyrrolidines would depend on the regioisomers of the we prepared a model of fullerene and metallofullerene mixture 10490 Chem. Commun., 2013, 49, 10489--10491 This journal is c The Royal Society of Chemistry 2013 View Article Online ChemComm Communication Notes and references 1 M. Yamada, T. Akasaka and S. Nagase, Acc. Chem. Res., 2009, 43, 92–102. 2 M. Garcia-Borra`s, S. Osuna, M. Swart, J. M. Luis, L. Echegoyen and M. Sola`, Chem. Commun., 2013, 49, 8767–8769. 3 M. Vizuete, M. Barrejo´n, M. J. Go´mez-Escalonilla and F. Langa, Nanoscale, 2012, 4, 4370–4381. 4A.A.Popov,S.YangandL.Dunsch,Chem. Rev.,2013,113, 5989–6113. 5 J. Zhang, S. Stevenson and H. C. Dorn, Acc. Chem. Res., 2013, 46, 1548–1557. 6 S. Yang, F. Liu, C. Chen, M. Jiao and T. Wei, Chem. Commun., 2011, 47, 11822–11839. 7 T. Zuo, K. Walker, M. M. Olmstead, F. Melin, B. C. Holloway, L. Echegoyen, H. C. Dorn, M. N. Chaur, C. J. Chancellor, C. M. Beavers, A. L. Balch and A. J. Athans, Chem. Commun., 2008, 1067–1069. Fig. 4 Separation of Sc3N@Ih-C80 from a mixture of Sc3N@Ih-C80,C60 and C70 8 P. P. Fatouros, F. D. Corwin, Z.-J. Chen, W. C.
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