biostudies-literatureDawson GANational Institute of General Medical SciencesNIGMS NIH HHSAir Force Office of Scientific Researche202411110https://www.ebi.ac.uk/biostudies/studies/S-EPMC11780508biostudies-literatureUnknown63(48)Bidentate N-ligands are paramount to recent advances in nickel-catalyzed cross-coupling reactions. Through comprehensive organometallic, spectroscopic, and computational studies on bi-oxazoline and imidazoline ligands, we reveal that a square planar geometry enables redox activity of these ligands in stabilizing nickel radical species. This finding contrasts with the prior assumption that bi-oxazoline lacks redox activity due to strong mesomeric donation. Moreover, we conducted systematic cyclic voltammetry (CV) analyses of bidentate pyridyl, oxazoline, and imidazoline nitrogen ligands, along with their corresponding nickel complexes. Complexation with nickel shifts the reduction potentials to a more positive region and narrows the differences in redox potentials among the ligands. AdditioAngewandte Chemie (International ed. in English)Redox Activity and Potentials of Bidentate N-Ligands Commonly Applied in Nickel-Catalyzed Cross-Coupling Reactions.PMC11780508R01 GM127778FA9550-20-1-0158Neary MCDawson GADiao TSeith MCfalseRedox Activity and Potentials of Bidentate N-Ligands Commonly Applied in Nickel-Catalyzed Cross-Coupling Reactions.Bidentate N-ligands are paramount to recent advances in nickel-catalyzed cross-coupling reactions. Through comprehensive organometallic, spectroscopic, and computational studies on bi-oxazoline and imidazoline ligands, we reveal that a square planar geometry enables redox activity of these ligands in stabilizing nickel radical species. This finding contrasts with the prior assumption that bi-oxazoline lacks redox activity due to strong mesomeric donation. Moreover, we conducted systematic cyclic voltammetry (CV) analyses of bidentate pyridyl, oxazoline, and imidazoline nitrogen ligands, along with their corresponding nickel complexes. Complexation with nickel shifts the reduction potentials to a more positive region and narrows the differences in redox potentials among the ligands. Additio2024-01-01T00:00:00Z2024 Nov2025-04-25T18:51:49.722Z2025-04-06T07:43:18.865ZS-EPMC117805083926426110.1002/anie.202411110