Fullerenes have found their main application in organic photovoltaic devices thanks to their ability to give rise a high efficient photo-induced electron transfer process and to their behaviour as n-type charge carriers.[1]

On the other hand, in face of the great interest for carbon based materials in catalysis, the use of fullerenes in this field has been completely neglected as probably due to the difficult to endow fullerene cages with suitable active sites. In this regards, as a first step to address this issue, we have reported recently a wide range of asymmetric metal mediated or organocatalytic methodologies for a precise stereocontrol in the fullerenes functionalizations.[2]

Herein, we present the enantioselective catalytic synthesis of fullerene hybrids where C₆₀ is endowed with metal atoms such us iridium, rhodium and ruthenium with high enantiomeric excesses. A complete control on the stereochemistry of all the asymmetric centers was achieved, even on the stereogenic metal center.[3]

The catalytic and photo-electrocatalytic properties of these new fullerene derivatives will be discussed together with their ability to transfer chirality in hydrogen transfer processes.[4]

[1] (a) B. C. Thompson, J. M. J. Fréchet, Angew. Chem. Int. Ed. 2008, 47, 58; (b) J. L. Delgado, P.-A. Bouit, S. Filippone, M. A. Herranz, N. Martin, Chem.Commun. 2010, 46, 4853.

[2] (a) Maroto, E. E.; Izquierdo, M.; Reboredo, S.; Marco-Martínez, J.; Filippone, S.; Martín, N. Acc. Chem. Res. 2014, 47, 2660. (b) Filippone, S.; Maroto, E. E.; Martín-Domenech, A.; Suárez, M.; Martín, N. Nat. Chem. 2009, 1, 578. (c) Maroto, E. E.; Mateos, J.; Garcia-Borràs, M.; Osuna, S.; Filippone, S.; Herranz, M. Á.; Murata, Y.; Solà, M.; Martín, N. J. Am. Chem. Soc. 2015, 137, 1190. (d) Marco-Martínez, J.; Reboredo, S.; Izquierdo, M.; Marcos, V.; López, J. L.; Filippone, S.; Martín, N. J. Am. Chem. Soc. 2014, 136, 2897. (e) Marco-Martínez, J.; Marcos, V.; Reboredo, S.; Filippone, S.; Martín, N. Angew. Chem. Int. Ed. 2013, 52, 5115.

[3] J. Marco-Martínez, S. Vidal, I. Fernández, S. Filippone and N. Martín, Angew. Chem. Int. Ed., 2017, 56, 2136.

[4] R. Maria Giron, J. Marco-Martinez, S. Bellani, A. Insuasty, H. Comas Rojas, G. Tullii, M. R. Antognazza, S. Filippone and N. Martin, J. Mater. Chem. A, 2016, 4, 14284.