Unraveling the catalytically preferential pathway between the direct and indirect hydrogenation of CO2to CH3OH using N-heterocyclic carbene-based Mn(i)catalysts: a theoretical approach

Abstract

CO2hydrogenation to CH3OH is a pivotal transformation for various reasons. A series of N-heterocyclic carbene (NHC)-based Mn-catalysts have been investigated using the density functional theoretical studies for the CO2hydrogenation to CH3OH. The catalytic hydrogenation of CO2to CH3OH can be achieved through direct and/or indirect mechanisms. In the present work, we have carried out both direct and indirect pathways for CO2hydrogenation to CH3OH in the presence of NHC-based Mn(i) catalysts. Various mechanistic pathways have been explored for the reaction. In this study, we show that NHC-based Mn(i) catalysts can be very promising for CO2hydrogenation due to the presence of the non-innocent NHC ligand, and these catalysts also favor the direct pathway over the indirect pathway for the CO2hydrogenation reaction. © The Royal Society of Chemistry 2021.