An In-Depth Mechanistic Study of Ru-Catalysed Aqueous Methanol Dehydrogenation and Prospects for Future Catalyst Design
| Autor: | Monica Trincado, Vivek Sinha, Hansjörg Grützmacher, Evert Jan Meijer, Bas de Bruin, Nitish Govindarajan |
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| Přispěvatelé: | Molecular Simulations (HIMS, FNWI), HIMS Other Research (FNWI), Homogeneous and Supramolecular Catalysis (HIMS, FNWI), Sustainable Chemistry, HCSC+ (HIMS, FNWI) |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
explicit solvent
Aqueous solution Hydrogen bond Hydride Organic Chemistry methanol dehydrogenation DFT-MD ligand pK(a) Combinatorial chemistry Catalysis Inorganic Chemistry Solvent chemistry.chemical_compound Catalytic cycle chemistry Reactivity (chemistry) Dehydrogenation Methanol Physical and Theoretical Chemistry |
| Zdroj: | ChemCatChem, 12 (9) ChemCatChem, 12(9), 2610-2621. Wiley |
| ISSN: | 1867-3880 1867-3899 |
| Popis: | Herein we provide mechanistic insights into the dehydrogenation of aqueous methanol catalysed by the [Ru(trop2dae)] complex (which is in‐situ generated from [Ru(trop2dad)], trop2dad=1,4‐bis(5H‐dibenzo[a,d]cyclohepten‐5‐yl)‐1,4‐diazabuta‐1,3‐diene), established by density functional theory based molecular dynamics (DFT‐MD) and static DFT calculations incorporating explicit solvent molecules. The aqueous solvent proved to participate actively in various stages of the catalytic cycle including the catalyst activation process, and the key reaction steps involving C−H activation and hydrogen production. The aqueous solvent forms an integral part of the reactive system for the C−H activation steps in the [Ru(trop2dae)] system, with strong hydrogen bond interactions with the anionic oxygen (RO−, R=CH3, CH2OH, HCO) and hydride moieties formed along the reaction pathway. In contrast to the [Ru(trop2dad)] catalyst, C−H activation and hydrogen production does not proceed via a metal‐ligand cooperative pathway for the [Ru(trop2dae)] system. The pKa of the coordinated amine donors in these complexes provides a rationale for the divergent reactivity, and the obtained mechanistic information provides new guidelines for the rational design of active and additive free catalytic systems for aqueous methanol dehydrogenation. ChemCatChem, 12 (9) ISSN:1867-3880 ISSN:1867-3899 |
| Databáze: | OpenAIRE |
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