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The selective activation of C−F bonds under mild reaction conditions remains an ongoing challenge of bond activation. Here, we present a cooperative [Rh/P(O)nBu2] template for catalytic hydrodefluorination (HDF) of perfluoroarenes. In addition to substrates presenting electron‐withdrawing functional groups, the system showed an exceedingly rare tolerance for electron‐donating functionalities and heterocycles. The high chemoselectivity of the catalyst and its readiness to be deployed at a preparative scale illustrate its practicality. Empirical mechanistic studies and a density functional theory (DFT) study have identified a rhodium(I) dihydride complex as a catalytically relevant species and the determining role of phosphine oxide as a cooperative fragment. Altogether, we demonstrate that molecular templates based on these design elements can be assembled to create catalysts with increased reactivity for challenging bond activations. [ABSTRACT FROM AUTHOR]

The selective activation of C−F bonds under mild reaction conditions remains an ongoing challenge of bond activation. Here, we present a cooperative [Rh/P(O)nBu2] template for catalytic hydrodefluorination (HDF) of perfluoroarenes. In addition to substrates presenting electron‐withdrawing functional groups, the system showed an exceedingly rare tolerance for electron‐donating functionalities and heterocycles. The high chemoselectivity of the catalyst and its readiness to be deployed at a preparative scale illustrate its practicality. Empirical mechanistic studies and a density functional theory (DFT) study have identified a rhodium(I) dihydride complex as a catalytically relevant species and the determining role of phosphine oxide as a cooperative fragment. Altogether, we demonstrate that molecular templates based on these design elements can be assembled to create catalysts with increased reactivity for challenging bond activations. [ABSTRACT FROM AUTHOR]