(4+2) and (2+2) Cycloadditions of Benzyne to C-60 and Zig-Zag Single-Walled Carbon Nanotubes: The Effect of the Curvature

Addition of benzyne to carbon nanostructures can proceed via (4 + 2) (1,4-addition) or (2 + 2) (1,2-addition) cycloadditions depending on the species under consideration. In this work, we analyze by means of density functional theory (DFT) calculations the reaction mechanisms for the (4 + 2) and (2 + 2) cycloadditions of benzyne to nanostructures of different curvature, namely, C-60 and a series of zigzag single-walled carbon nanotubes. Our DFT calculations reveal that, except for the concerted (4 + 2) cycloaddition of benzyne to zigzag single-walled carbon nanotubes, all cycloadditions studied are stepwise processes with the initial formation of a biradical singly bonded intermediate. From this intermediate, the rotation of the benzyne moiety determines the course of the reaction. The Gibbs energy profiles lead to the following conclusions: (1) except for the 1,4-addition of benzyne to a six-membered ring of C-60, all 1,2- and 1,4-additions studied are exothermic processes; (ii) for C-60 the (2 + 2) benzyne cycloaddition is the most favored reaction pathway; (iii) for zigzag single-walled carbon nanotubes, the (4 + 2) benzyne cycloaddition is preferred over the (2 + 2) reaction pathway; and (iv) there is a gradual decrease in the exothermicity of the reaction and an increase of energy barriers as the diameter of the nanostructure of carbon is increased. By making use of the activation strain model, it is found that the deformation of the initial reactants in the rate-determining transition state is the key factor determining the chemoselectivity of the cycloadditions with benzyne