Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts

to FA and MeOH and the dehydrogenation of FA and MeOH and provide a brief comparison between precious metal and base metal systems. We highlight the different ligands that have been used to stabilize first row transition metal catalysts and discuss the use of additives to promote catalytic activity. In particular, the Account focuses on the crucial role that alkali metal Lewis acid cocatalysts can play in promoting increased activity and catalyst stability for first row transition metal systems. We relate these effects to the nature of the elementary steps in the catalytic cycle and describe how the Lewis acids stabilize the crucial transition states. For all four transformations, we discuss in detail the currently proposed catalytic pathways, and throughout the Account we identify mechanistic similarities among catalysts for the four processes. The limitations of current catalytic systems are detailed, and suggestions are provided on the improvements that are likely required to develop catalysts that are more stable, active, and practical.