Reaction mechanisms of the Rh-catalyzed dehydrogenative aryl–aryl bond formation reaction of tertiary benzamide with bromobenzene: A theoretical study

•PivO− anion plays an important role in activating the C–H bond.•The second C–H bond activation step is the rate-limiting step.•Meta product was obtained as a major product due to the steric effects.

Density functional theory calculations were performed to understand the detailed mechanisms of Rh-catalyzed dehydrogenative aryl–aryl bond formation reactions. The calculated results show that the reaction undergoes three steps: two consecutive C–H bond activations followed by the final reductive elimination. Our theoretical study indicates that PivO− anion plays an important role in activating the C–H bond. In addition, the regioselectivity of C–H bond activation has been explored in this work. Meta product was obtained as a major product and para product as a minor product mainly due to the electronic and steric effects.

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