A DFT study on Diels-Alder cycloadditions oftrans-1,3-butadiene to C60and C70

Abstract

Investigation of the relative reactivity of bonds in fullerenes will provide fundamental theory for the design of fullerene-based materials. We have theoretically investigated the reactivity of the Diels–Alder (DA) cycloaddition of cis-1,3-butadiene to all types of bonds in C60 and C70 using the M06-2X hybrid density functional theory (DFT) calculations (J. Phys. Org. Chem. 2012, 25 850–855) and have pointed out that the DA cycloadditions of cis and trans forms of 1,3-butadiene to ethylene have a specially intimate relationship (J. Phys. Org. Chem. 2014, 27 652–660). For the aim of telling a whole story of the DA cycloaddition concerning C60 and C70, the DA cycloadditions of trans-1,3-butadiene to all types of bonds in C60 and C70 were explored at the same theoretical level as those of the cis-1,3-butadiene. The calculated results related with the trans- and cis-1,3-butadienes were compared. The potential energy curves of DA cycloadditions of trans- and cis-1,3-butadiene to C60 and C70 were discussed. The distortion–interaction energy model was employed to elucidate the origin of different reactivity of all kinds of CC bonds. The solvent effects were examined using the continuum solvent model. These current results, along with our previous research, will help to obtain an overall view of the DA cycloadditions of 1,3-butadiene to C60 and C70. Copyright © 2014 John Wiley & Sons, Ltd.