title: Understanding the reactivity of endohedral metallofullerenes: C78 versus Sc3N@C78.
abstract: The physical factors behind the reduced Diels-Alder reactivity of the Sc3N@C78 metallofullerene as compared with free C78 have been investigated in detail by means of computational tools. To this end, the reactions between 1,3-butadiene and free C78 and endohedral Sc3N@C78 have been analysed in terms of regioselectivity and reactivity by using the activation strain model of reactivity in combination with the energy decomposition analysis method. Additional factors such as the molecular orbital overlap or the aromaticity of the corresponding transition states have been also explored. Our results indicate that the lower reactivity of the metallofullerene finds its origin mainly in the less stabilizing interaction between the deformed reactants along the reaction coordinate induced by the triscandium nitride moiety.
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), VU University, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands); Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (The Netherlands).
authors.forename: F Matthias
authors.initials: FM
authors.lastname: Bickelhaupt
authors.forename: Miquel
authors.initials: M
authors.lastname: Solà
authors.forename: Israel
authors.initials: I
authors.lastname: Fernández
keywords: aromaticity; cycloaddition; density functional calculations; fullerenes; regioselectivity