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Download fileUnraveling Metal/Pincer Ligand Effects in the Catalytic Hydrogenation of Carbon Dioxide to Formate
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posted on 20.11.2018, 19:50 authored by Boodsarin Sawatlon, Matthew D. Wodrich, Clémence CorminboeufThe hydrogenation
of carbon dioxide to formate is an intriguing
reaction from both an environmental and an energy perspective, primarily
due to the prospective uses of the product as a platform chemical
in numerous applications such as an organic hydrogen carrier. Although
several transition-metal-based catalysts have been shown to facilitate
this chemical transformation, few guidelines exist on how best to
tune the catalysts in order to achieve maximum activity. Here, we
use linear scaling relationships and molecular volcano plots to gauge
the potential of different metal–pincer catalysts for the aforementioned
reaction. Analysis of combinations of five metals (Ru, Os, Co, Rh,
and Ir) and seven tridentate pincer-type ligands reveals several complexes
lying near the volcano top, suggesting that these species have nearly
ideal energetic profiles for facilitating the hydrogenation reaction.
In particular, catalysts bearing group 9 metal centers (Ir, Rh, Co)
with π-acidic ligands provide a clear route to improving catalytic
activity. Overall, these findings highlight how linear scaling relationships
and molecular volcano plots provide unique insight into the underlying
stereoelectronic factors that make specific metal–ligand combinations
highly efficient catalysts.