Mechanism of Iridium-Mediated Selective Arene Cleavage: Insights from Density Functional Theory (DFT) Calculations.

The mechanism and regioselectivity of iridium-mediated cleavage of aromatic C-C bonds in a series of monomethylated, dimethylated, and trimethylated benzenes without the activation of weaker C-H and C-C bonds are clarified using density functional theory (DFT) calculations. The calculations explained why the reactivity of the coordinated arene in the observed C-C bond cleavage reaction decreases as the degree of substitution decreases.