Photoexcited Pd(ii) auxiliaries enable light-induced control in C(sp(3))–H bond functionalisation

Herein we report the photophysical and photochemical properties of palladacycle complexes derived from 8-aminoquinoline ligands, commonly used auxiliaries in C–H activation. Spectroscopic, electrochemical and computational studies reveal that visible light irradiation induces a mixed LLCT/MLCT charge transfer providing access to synthetically relevant Pd(iii)/Pd(iv) redox couples. The Pd(ii) complex undergoes photoinduced electron transfer with alkyl halides generating C(sp(3))–H halogenation products rather than C–C bond adducts. Online photochemical ESI-MS analysis implicates participation of a mononuclear Pd(iii) species which promotes C–X bond formation via a distinct Pd(iii)/Pd(iv) pathway. To demonstrate the synthetic utility, we developed a general method for inert C(sp(3))–H bond bromination, chlorination and iodination with alkyl halides. This new strategy in auxiliary-directed C–H activation provides predictable and controllable access to distinct reactivity pathways proceeding via Pd(iii)/Pd(iv) redox couples induced by visible light irradiation.