Capturing the Complete Reaction Profile of a C–H Bond Activation

Abstract

The activation of C-H bonds requires the generation of extremely reactive species, which hinders the study of this reaction and its key intermediates. To overcome this challenge, we synthesized an iron(III) chloride-pyridinediimine complex that generates a chlorine radical proximate to reactive C-H bonds upon irradiation with light. Transient spectroscopy confirms the formation of a Cl center dot|arene complex, which then activates C-H bonds on the PDI ligand to yield HCl and a carbon-centered radical as determined by photocrystallography. First-principles molecular dynamics-density functional theory calculations reveal the trajectory for the formation of a Cl center dot|arene intermediate. Together, these experimental and computational results show the complete reaction profile for the preferential activation of a C-H bond in the solid state.