A complete guide on the influence of metal clusters in the diels-alder regioselectivity of Ih-C80 endohedral metallofullerenes

The chemical functionalization of endohedral metallofullerenes (EMFs) has aroused considerable interest due to the possibility of synthesizing new species with potential applications in materials science and medicine. Experimental and theoretical studies on the reactivity of endohedral metallofullerenes are scarce. To improve our understanding of the endohedral metallofullerene reactivity, we have systematically studied with DFT methods the Diels-Alder cycloaddition between s-cis-1,3-butadiene and practically all X@I h-C80 EMFs synthesized to date: X=Sc3N, Lu 3N, Y3N, La2, Y3, Sc 3C2, Sc4C2, Sc3CH, Sc3NC, Sc4O2 and Sc4O3. We have studied both the thermodynamic and kinetic regioselectivity, taking into account the free rotation of the metallic cluster inside the fullerene. This systematic study has been made possible through the use of the frozen cage model (FCM), a computationally cheap approach to accurately predicting the exohedral regioselectivity of cycloaddition reactions in EMFs. Our results show that the EMFs are less reactive than the hollow Ih-C80 cage. Except for the Y3 cluster, the additions occur predominantly at the [5,6] bond. In many cases, however, a mixture of the two possible regioisomers is predicted. In general, [6,6] addition is favored in EMFs that have a larger charge transfer from the metal cluster to the cage or a voluminous metal cluster inside. The present guide represents the first complete and exhaustive investigation of the reactivity of Ih-C80-based EMFsWe are grateful for financial support from the Spanish MICINN (projects CTQ2011-23156/BQU and CTQ2011-25086/BQU), the Catalan DIUE (projects 2009SGR637, 2009SGR528, and XRQTC), and the FEDER fund (grant UNGI08-4E-003). M.G.-B. thanks the Spanish MECD for a Ph. D. fellowship (AP2010-2517) and S.O. thanks the European Community for a postdoctoral fellowship (PIOF-GA-2009-252856). Excellent service by CESCA is acknowledged. The authors are also grateful to the computer resources and assistance provided by the BSC-CNS. M.S. thanks the Catalan DIUE for the ICREA Academia 2009 Awar