Photoexcited Pd(ii) auxiliaries enable light-induced control in C(sp(3))-H bond functionalisation
AuthorCzyz, ML; Weragoda, GK; Horngren, TH; Connell, TU; Gomez, D; O'Hair, RAJ; Polyzos, A
Source TitleChemical Science
PublisherROYAL SOC CHEMISTRY
University of Melbourne Author/sPolyzos, Anastasios; Czyz, Milena; O'Hair, Richard; Gomez, Daniel; Weragoda, Geethika; Horngren, Tyra
AffiliationSchool of Chemistry
School of Physics
Document TypeJournal Article
CitationsCzyz, M. L., Weragoda, G. K., Horngren, T. H., Connell, T. U., Gomez, D., O'Hair, R. A. J. & Polyzos, A. (2020). Photoexcited Pd(ii) auxiliaries enable light-induced control in C(sp(3))-H bond functionalisation. CHEMICAL SCIENCE, 11 (9), pp.2455-2463. https://doi.org/10.1039/c9sc05722f.
Access StatusOpen Access
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.
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