Journal
ORGANOMETALLICS
Volume 36, Issue 24, Pages 4908-4919Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.7b00761
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Funding
- SINERGIA project (SNF project) [CRSII2_154448]
- CSCS production projects [CH5, S629]
- Holcim Foundation
- Swiss National Science Foundation (SNF) [CRSII2_154448] Funding Source: Swiss National Science Foundation (SNF)
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Reaction pathways relevant to the CO2 hydrogenation to formate using a homogeneous (IrH3)-H-III(PNP) pincer catalyst have been investigated using static DFT calculations and ab initio molecular dynamics simulations under reaction conditions. The role of a base, solvent, and the noninnocent ligand are demonstrated. Static DFT calculations with an implicit solvent highlight the importance of selecting a highly polar solvent. The insertion of CO2 and regeneration of the catalyst are identified as the key steps in the reaction mechanism. Unlike in the static DFT calculations, the AIMD simulations show that an additional CO2 molecule and explicit water molecules can expedite the direct cleavage of the H-2 coordinated to the metal center to regenerate the catalyst. In addition, the AIMD simulations indicate that the pyridine ring does not participate in the hydrogenation mechanism, while the alpha-carbon at the pyridine ring is very acidic and participates in off-cycle reactions.
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