The development of Rhenium I photocatalysts has been pursued since Lehn first showed the excellent performance of the ReI bipyridine tricarbonyl catalyst. Since then, devel- opment has modified the organic ligand to demonstrate continued or improved activity with other α-diimine bidentate geometries. Geometry has been limited to bidentate motifs, with fac-(CO)3 and axial halides. This work will demonstrate the synthesis, characterization, and testing of a new terdentate, κ3(L3)−Re1(CO)2X (X = Cl, Br, CN, OTf) family of compounds for CO2 reduction, as well as computational investigations into the mechanism of the reduction of CO2 to CO and other species. Development of computational aides will be described as well.