Endohedral Fullerenes Bis-Adducts: Regio-Chemistry Control Directed By the Cluster inside

Monday, 25 May 2015: 09:20
Lake Ontario (Hilton Chicago)
M. R. Cerón (University of Texas at El Paso), M. Izquierdo (Universidad Complutense de Madrid), and L. Echegoyen (University of Texas at El Paso)
Exohedral functionalization of endohedral fullerenes is essential to increase their solubility and explore their properties and potential applications in nanomaterial science.[i] At the present, few bis-derivatives have been reported, mainly because of the low yields and large number of isomeric products obtained.[ii] Dorn et al. and Akasaka et al. suggested than bis-adduct formation appears to be controlled by the metal or metallic cluster inside. Here we report the use of a well known method (tether-directed remote multifunctionalization)[iii] for the bis-functionalization of new endohedral fullerene bis-derivatives and compare the results to those observed for independent bis-pyrrolidine additions.

Figure 1. a) Bis-adduct derivative of M3N@Ih-C80 using the tether-directed remote multifunctionalization method (M = Lu, Sc). b) Bis-pyrrolidine derivative of M3N@Ih-C80 using two independent additions (M = Lu, Sc).

[i](a) M. N. Chaur, F. Melin, A. L. Ortiz, L. Echegoyen, M. N. Chaur, F. Melin, A. L. Ortiz, L. Echegoyen, Angew. Chem. Int. Ed. 2009, 48, 7514-7538 (b) D. M. Rivera-Nazario, J. R. Pinzón, S. Stevenson, L. A. Echegoyen, J. Phys. Org. Chem. 2013, 26, 194-205 (c) M. R. Cerón, F.-F. Li, L. Echegoyen, J. Phys. Org. Chem. 2014, 27, 258-264.

[ii](a) S. Stevenson, R. R. Stephen, T. M. Amos, V. R. Cadorette, J. E. Reid, J. P. Phillips, J. Am. Chem. Soc. 2005, 127, 12776-12777 (b) T. Cai, L. Xu, C. Shu, H. A. Champion, J. E. Reid, C. Anklin, M. R. Anderson, H. W. Gibson, H. C. Dorn, J. Am. Chem. Soc. 2008, 130, 2136-2137 (c) M. O. Ishitsuka, S. Sano, H. Enoki, S. Sato, H. Nikawa, T. Tsuchiya, Z. Slanina, N. Mizorogi, M. T. H. Liu, T. Akasaka, S. Nagase, J. Am. Chem. Soc. 2011, 133, 7128-7134.

[iii]C. Thilgen, F. Diederich, Chem. Rev. 2006, 106, 5049-5135.