Based on the mechanism study of hydrogenation of carbon dioxide catalyzed by (PNP)IrH3 (PNP = 2,6-bis(di-iso-propylphosphinomethyl)pyridine), two PNP-ligated base metal complexes, trans-(PNP)Fe(H)2CO and (PNP)CoH3 were computationally designed as potential low-cost catalysts for hydrogenation of carbon dioxide. For the formation of formic acid from H2 and CO2 catalyzed by (PNP)IrH3, trans-(PNP)Fe(H)2CO and (PNP)CoH3, the reaction pathways with direct H2 cleavage by OH� without the participation of the PNP ligand are about 20 kcal/mol more favorable than a previously postulated mechanism that involves the aromatization and dearomatization of the pyridine ring in the PNP ligand for H2 cleavage. This finding reveals the essential role of a base in CO2 reduction and suggests that the incorporation of strong bases and unsaturated ligands may be critical for the design of new catalyst for hydrogen activation and low energy proton transfers.

Mechanistic insights and computational design of base metal catalysts for hydrogenation of carbon dioxide

246th National Meeting (2013)

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