Role of Water, CO2, and Noninnocent Ligands in the CO2 Hydrogenation to Formate by an Ir(III) PNP Pincer Catalyst Evaluated by Static-DFT and ab Initio Molecular Dynamics under Reaction Conditions
| العنوان: | Role of Water, CO2, and Noninnocent Ligands in the CO2 Hydrogenation to Formate by an Ir(III) PNP Pincer Catalyst Evaluated by Static-DFT and ab Initio Molecular Dynamics under Reaction Conditions |
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| المؤلفون: | Aleix Comas-Vives, C. S. Praveen, Joost VandeVondele, Christophe Copéret |
| المصدر: | Organometallics. 36:4908-4919 |
| بيانات النشر: | American Chemical Society (ACS), 2017. |
| سنة النشر: | 2017 |
| مصطلحات موضوعية: | inorganic chemicals, Reaction mechanism, 010405 organic chemistry, Ligand, Organic Chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, 0104 chemical sciences, Pincer movement, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Computational chemistry, Pyridine, Molecule, Formate, Physical and Theoretical Chemistry |
| الوصف: | Reaction pathways relevant to the CO2 hydrogenation to formate using a homogeneous IrIIIH3(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 H2 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 α-carbon at the pyridine ring is very acidic and participates in off-cycle reactions. |
| تدمد: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.7b00761 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::a51b6e577c0b0f6c0b02376e48e58c6c https://doi.org/10.1021/acs.organomet.7b00761 |
| رقم الانضمام: | edsair.doi...........a51b6e577c0b0f6c0b02376e48e58c6c |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15206041 02767333 |
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| DOI: | 10.1021/acs.organomet.7b00761 |