Metallofullerenes: Structure, isomerism, reactivity and properties

The characterisation of the most novel metallofullerenes up to 2004 has been theoretically and systematically discussed in this Ph-D thesis presented in 2005 at Universitat Rovira i Virgili and reissued in 2011. From the structural point of view, metallofullerenes can be divided into three main groups according to the metal position: endohedral, heterohedral and exohedral metallofullerenes. The main families of compounds studied are Sc3-nMnN@Ck (n = 0-3, M = Y, La; k = 68, 78, 80) for endohedrals, CxMn (x = 56, 57, 58, 59; M = Pt, Ir, Os; n = 1, 2) for heterohedrals and Ck-{M(PH3)2}n (k = 60, 70, 84; M = Pt, Pd, Ni; n = 1, 2, 4, 6) for exohedrals. The present research is a step forward in the knowledge of each of these families of compounds, and in particular, in our understanding of the metal-carbon bond, isomerism and reactivity. The DFT method proved to be an excellent computational tool for providing good geometries, for solving the intricacies of the different metal-carbon bonds, for reproducing experimental data (ionization potentials and electron affinities) and also for making predictions about isomerism stability and reactivity.