Chemistry Reference
In-Depth Information
Fig. 4.5
Representation of the
D
3h
-C
78
free cage LUMO, LUMO
+
1 and LUMO
+
3 (isosurface
value 0.02 a.u.) in which only those bonds with favorable orbitals to interact with the HOMO of the
diene are marked with
ellipses
. For comparison the same information is given for Ti
2
C
2
@
D
3h
-C
78
.
(Reprinted with permission from (Garcia-Borràs et al.
2012a
). Copyright 2012 Wiley)
due to the encapsulation of metallic clusters (fullerene strain, charge transfer, etc.)
are much more important than the simplest rules based on the C-C bond distances,
pyramidalization angles or LUMO orbitals shape. There exists not (yet) a predictive
indicator of the most suitable addition sites, but we can rationalize the observed
behavior based on the analysis of the metallic cluster effects.
4.2.2
The Diels-Alder Cycloaddition on I
h
-C
80
versus D
5h
-C
80
Endohedral M
3
N(M
=
Sc, Lu, Gd) Metallofullerenes
The computational exploration of the exohedral reactivity of EMFs has been shown
to be a powerful tool to understand, predict and give support to the experimental
addition sites (Osuna et al.
2011a
). We decided to provide a detailed investigation of
