An efficient visible light induced rhodium(I)catalyzedr egioselective borylation of aromatic C À Hb onds is reported. The photocatalytic system is based on asingle NHC À Rh I complex capable of both harvesting visible light and enabling the bond breaking/forming at room temperature.The chelating nature of the NHC-carboxylate ligand was critical to ensure the stability of the Rh I complex and to provide excellent photocatalytic activities.E xperimental mechanistic studies evidenced ap hotooxidative ortho C À Hb ond addition upon irradiation with blue LEDs,leading to acyclometalated Rh IIIhydride intermediate.
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