CO2 is generally regarded as a waste product. However, the efficient catalytic reduction of CO2 means that this concept can change to viewing this molecule as a feedstock to produce chemically valuable products. The catalytic reduction of CO2 is a challenge because of its stability, and its reduction into chemically valuable products requires an appropriate catalyst and accessible energy source. While second and third row transition metals have shown considerable promise as photocatalysts for the reduction of CO2 to CO, one of our goals is to elaborate on the metal centers and the ligand environments in order to discover new catalysts and processes. These efforts have revealed new photocatalysts based on manganese and rhenium supported by κ2-PN phosphinoaminopyridine ligands. This thesis will describe the synthesis and characterization of these catalysts and their CO2 reduction parameters. The selectivity of these catalysts for either CO or HCOOH will be explored. Furthermore, ligand modifications and their effects on the catalyst behaviour will also be presented.