The fundamental challenge of reducing CO, into more valuable energy-containing compounds depends on revealing new catalysts for this process. By removal of the long-standing limitation of alpha-diimine ligation, which is dominant in photocatalytic complexes in this area, new visible-light, CO2-reducing photocatalysts based on Mn and Re supported by kappa(2)-PN phosphinoaminopyridine ligands were identified. These catalysts, [M{kappa(2)-(Ph2P)NH(NC5H4)}(CO)(3)Br], displayed excellent product selectivity and, by a change of only the metal center, gave a dramatic product switch from CO with M = Mn to HCO2H with M = Re. The catalyst systems were explored with variation of the ligand, electron donor, solvent, and photosensitizer. The products were definitively traced using (CO2)-C-13 as a substrate. Both complexes quenched the excited-state photosensitizer Ru(bpy)(3)(2+)*, suggesting oxidative quenching as a potential entry into the catalytic cycle.