First‐Principles Insights into the Mechanism of CO2 Hydrogenation Reactions by Fe‐PNP Pincer Complex

Abstract

AbstractUsing the state of the art theoretical methods, we have provided a comprehensive mechanistic understanding of the CO2 hydrogenation into HCOOH, H2CO, and CH3OH by 2,6‐bis(diisopropylphosphinomethyl)pyridine (PNP)‐ligated Fe pincer complex, featuring one CO and two H as co‐ligands. For the computational investigation, a verified structural model containing methyl groups in place of the experimental isopropyl groups was used. Three catalytic conversions involving hydrogenation of CO2 into formic acid (HCOOH), HCOOH into formaldehyde and methanol were studied in different solvent medium. Our modelled complex appears to be a viable base‐free catalyst for the conversion of CO2 into HCOOH and HCOOH into H2CO, based on the free energy profiles, which show apparent activation energy barriers of 16.28 kcal/mol and 23.63 kcal/mol for the CO2 to HCOOH and HCOOH to H2CO conversion, respectively. However, the computed results show that, due to the huge energy span of H2CO to CH3OH conversion, complete hydrogenation of CO2 into methanol could not occur under moderate conditions. Morpholine co‐catalyst, which can lower the hydrogenation barrier by taking part in a simultaneous H‐atom donation‐acceptance process, could have assisted in completing this step.