The Ir III /Ni II metallaphotoredox-catalyzed enantioselective cross-coupling of chiral α-(hetero)aryl amines was systematically investigated using density functional theory (DFT) calculations. Both oxidative-quenching (Ir III -*Ir III -Ir IV -Ir III ) and reductivequenching (Ir III -*Ir III -Ir II -Ir III ) photoredox cycles were found to be compatible with the nickel catalytic cycle (Ni II -Ni I -Ni III -Ni II ).Mechanistic analysis indicates that the overall transformation proceeds through three fundamental steps: single-electron transfer, oxidative addition, and stepwise outer-sphere reductive elimination, with oxidative addition identified as the ratedetermining step. Notably, the enantio-determining C⎯C bond-forming event occurs via an ion-pair intermediate embedded within the outer-sphere reductive-elimination pathway. Furthermore, the high enantioselectivity of the process originates predominantly from steric interactions between the substrate and the chiral ligand. These insights clarify the mechanistic basis of this photoredox-mediated dual-catalytic asymmetric transformation and may guide the design of next-generation metallaphotoredox asymmetric methodologies.

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