Hydrogenative Carbon Dioxide Reduction Catalyzed by Mononuclear Ruthenium Polypyridyl Complexes: Discerning between Electronic and Steric Effects
<p> The preparation and isolation of a family of new Ru-Cl complexes containing the deprotonated anionic tridentate meridional ligand (1Z,3Z)-N1,N3-di(pyridin-2-yl)isoindoline-1,3-diimine (Hbid) and 1,3-di(2-pyridyl)benzene) (Hdpb) namely, [Ru(bid)(acac)Cl], 1d, [Ru(bid)(6,6’-Me2-bpy...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2017 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2072/305771 |
| Acceso en línea: | http://hdl.handle.net/2072/305771 https://doi.org/10.1021/acscatal.7b00603 |
| Access Level: | acceso abierto |
| Palabra clave: | catalytic carbon dioxide reduction catalytic carbon dioxide hydrogenation ruthenium polypyridyl complexes transition metal redox properties DFT |
| Sumario: | <p> The preparation and isolation of a family of new Ru-Cl complexes containing the deprotonated anionic tridentate meridional ligand (1Z,3Z)-N1,N3-di(pyridin-2-yl)isoindoline-1,3-diimine (Hbid) and 1,3-di(2-pyridyl)benzene) (Hdpb) namely, [Ru(bid)(acac)Cl], 1d, [Ru(bid)(6,6’-Me2-bpy)Cl], 1e, trans-[Ru(bid)(py)2Cl], 2, [Ru(dpb)(bpy)Cl], 3a, and [Ru(dpb)(4,4’-(COOEt)2-bpy)Cl], 3b is reported. All these complexes have been thoroughly characterized in solution by NMR spectroscopy and for 1d and 1e by single crystal X-ray diffraction analysis. Furthermore, the redox properties of all complexes have been investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The capacity of the various complexes to catalyze hydrogenative CO2 reduction was also investigated. Compound 1e is the best catalyst, achieving initial turnover frequencies above 1000 h–1. Kinetic analysis identifies a relationship between Ru(III/II) couple redox potentials and initial turnover frequencies. Finally, DFT calculations further characterize the catalytic cycle of these complexes and rationalize electronic and steric effects deriving from the auxiliary ligands.</p> <p> </p> |
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