Photoexcited Pd(ii) auxiliaries enable light-induced control in C(sp3)–H bond functionalisation

Abstract

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(sp³)–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(sp³)–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.