Abstract
Direct hydrogenation of carbon dioxide to methanol is an important goal for sustainability. The ruthenium-triphos complex was reported to be successful in achieving this transformation. However, a reliable free energy profile able to explain the experimental kinetics has not been published yet. This work presents a detailed investigation of this transformation using the accurate ωB97M-V functional, followed by a detailed microkinetic analysis. We have found two key intermediates. The first one is [(triphos)Ru(HCOO)(THF)]+, named MS5 and formed at the beginning of the catalyzed reaction. The second, and the most stable, is [(triphos)Ru(HCOO)(CH3OH)]+, named MS22 and formed later in the reaction time. The highest barrier in the catalytic cycle (28.1 kcal mol−1) corresponds to the steps MS22 → [(triphos)Ru(H)(H2)(THF)]+ → TS4, with TS4 being the hydride transfer to the coordinated formate. Formic acid released in the catalysis can participate in the important proton transfer steps along the catalytic cycle.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
