Abstract: Catalysis with Earth-abundant transition metals (iron, cobalt, and nickel) offers myriad opportunities for improved sustainability, applications, and fundamental mechanistic organometallic chemistry. Our laboratory is actively exploring ways the flow of electrons with first-row transition metals can be leveraged for new applications in homogeneous catalysis as applied to organic and commodity chemical synthesis. Bis(phosphine) cobalt catalysts across three oxidation states have been synthesized and characterized that are highly active and enantioselective for the asymmetric hydrogenation of alkenes relevant to drug synthesis. Spectroscopic investigations in collaboration with Argonne scientists established an unusual pathway where the Co(II) oxidation state is maintained and the dehydrogenation methanol accompanied productive formation of alkane. In related chemistry, we have applied cobalt catalysts with redox-active ligands to the diboration of alkynes to yield the stereodefined diboryl alkenes. These molecules serve as interesting substrates for asymmetric hydrogenation and versatile building blocks for organic synthesis. These applications and others that leverage the unique electronic properties of first-row transition metals will be presented.