Rationalizing the AlI -Promoted Oxidative Addition of C-C Versus C-H Bonds in Arenes.

The factors controlling the oxidative addition of C-C and C-H bonds in arenes mediated by AlI have been computationally explored by means of Density Functional Theory calculations. To this end, we compared the processes involving benzene, naphthalene and anthracene which are promoted by a recently prepared anionic AlI -carbenoid. It is found that this species exhibits a strong tendency to oxidatively activate C-H bonds over C-C bonds, with the notable exception of benzene, where the C-C bond activation is feasible but only under kinetic control reaction conditions. State-of-the-art computational methods based on the combination of the Activation Strain Model of reactivity and the Energy Decomposition Analysis have been used to rationalize the competition between both bond activation reactions as well as to quantitatively analyze in detail the ultimate factors controlling these transformations.