Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
In this work, we study the trans influence of boryl ligands and other commonly used non-boryl ligands in order to search for a more active catalyst than the ruthenium dihydride complex Ru(PNP)(CO)H<sub>2</sub> for the hydrogenation of CO<sub>2</sub>. The theoretical calculati...
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| Autores principales: | , , , , |
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| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
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| Materias: | |
| Acceso en línea: | https://doaj.org/article/7957470d1f50467aa4fdda62a4fb2d1d |
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| Sumario: | In this work, we study the trans influence of boryl ligands and other commonly used non-boryl ligands in order to search for a more active catalyst than the ruthenium dihydride complex Ru(PNP)(CO)H<sub>2</sub> for the hydrogenation of CO<sub>2</sub>. The theoretical calculation results show that only the B ligands exhibit a stronger trans influence than the hydride ligand and are along increasing order of trans influence as follows: –H < –BBr<sub>2</sub> < –BCl<sub>2</sub> ≈ –B(OCH)<sub>2</sub> < –Bcat < –B(OCH<sub>2</sub>)<sub>2</sub> ≈ –B(OH)<sub>2</sub> < –Bpin < –B(NHCH<sub>2</sub>)<sub>2</sub> < –B(OCH<sub>3</sub>)<sub>2</sub> < –B(CH<sub>3</sub>)<sub>2</sub> < –BH<sub>2</sub>. The computed activation free energy for the direct hydride addition to CO<sub>2</sub> and the NBO analysis of the property of the Ru–H bond indicate that the activity of the hydride can be enhanced by the strong trans influence of the B ligands through the change in the Ru–H bond property. The function of the strong trans influence of B ligands is to decrease the d orbital component of Ru in the Ru–H bond. The design of a more active catalyst than the Ru(PNP)(CO)H<sub>2</sub> complex is possible. |
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