Cycloaddition of Benzyne to Armchair Single-Walled Carbon Nanotubes: [2 + 2] or [4 + 2]?

The reaction mechanism and regioselectivity of cycloaddition reactions of benzyne to armchair single-walled carbon nanotubes were investigated with quantum chemical methods. The [2 + 2] cycloaddition reaction follows the diradical mechanism, whereas the [4 + 2] cycloaddition reaction adopts the concerted mechanism. More importantly, the [2 + 2] product is always more stable thermodynamically than the [4 + 2] ones, regardless of the diameter, while the [4 + 2] cycloaddition becomes kinetically more favored as the diameter goes up.