Understanding the Influence of Lewis Acids on CO<sub>2</sub> Hydrogenation: The Critical Effect Is on Formate Rotation
Ljiljana Pavlovic, Kathrin H. Hopmann
Abstract
High Resolution Image Download MS PowerPoint Slide Lewis acids (LAs) have been shown to accelerate hydrogenation of CO 2, but the underlying mechanistic details remain to be elucidated. We have employed computational methods to investigate how LAs affect CO 2 hydrogenation with a range of known metal-hydrides (L n Ir–H, L n Ru–H, L n Mn–H, L n Co–H). Our results show that LAs can alter the nature of the hydride–CO 2 bond formation step, but do not lower its barrier. Instead, the accelerating effect of LAs is on the subsequent step, the rearrangement of the metal-formate σ-intermediate. These insights are essential for understanding the effect of LA additives on metal-mediated hydrogenations of CO 2 .
Topics & Concepts
ChemistryFormateHydrideLewis acids and basesMethyl formateMetalMedicinal chemistryOrganic chemistryCatalysisComputational chemistryCarbon dioxide utilization in catalysisCO2 Reduction Techniques and CatalystsCatalysis for Biomass Conversion