Elucidating the Mechanism of Excited-State Bond Homolysis in Nickel-Bipyridine Photoredox Catalysts.

ABSTRACT: Ni 2,2'-bipyridine (bpy) complexes are commonly employed photoredox catalysts of bond-forming reactions in organic chemistry. However, the mechanisms by which they operate are still under investigation. One potential mode of catalysis is via entry into Ni(I)/Ni(III) cycles, which can be made possible by light-induced, excited-state Ni(II)-C bond homolysis. Here, we report experimental and computational analyses of a library of Ni(II)-bpy aryl halide complexes, Ni(^Rbpy)(^R'Ph)Cl (R = MeO, t-Bu, H, MeOOC; R' = CH₃, H, OMe, F, CF₃), to illuminate the mechanism of excited-state bond homolysis. At given excitation wavelengths, photochemical homolysis rate constants span 2 orders of magnitude across these structures and correlate linea

SUBMITTER: Cagan DA 

PROVIDER: S-EPMC9979631 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature