title: A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures.
abstract: The development of an efficient catalytic process that mimics the enzymatic function of alcohol dehydrogenase is critical for using biomass alcohols for both the production of H2 as a chemical energy carrier and fine chemicals under waste-free conditions. Dehydrogenation of alcohol-water mixtures into their corresponding acids with molecular hydrogen as the sole by-product from the reaction can be catalysed by a ruthenium complex with a chelating bis(olefin) diazadiene ligand. This complex, [K(dme)2][Ru(H)(trop2dad)], stores up to two equivalents of hydrogen intramolecularly, and catalyses the production of H2 from alcohols in the presence of water and a base under homogeneous conditions. The conversion of a MeOH-H2O mixture proceeds selectively to CO2/H2 gas formation under neutral conditions, thereby allowing the use of the entire hydrogen content (12% by weight). Isolation and characterization of the ruthenium complexes from these reactions suggested a mechanistic scenario in which the trop2dad ligand behaves as a chemically 'non-innocent' co-operative ligand.
authors.affiliation: ETH Zürich, Department of Chemistry and Applied Biosciences, 8093 Zürich, Switzerland.
authors.forename: Rafael E
authors.initials: RE
authors.lastname: Rodríguez-Lugo
authors.forename: Mónica
authors.initials: M
authors.lastname: Trincado
authors.forename: Matthias
authors.initials: M
authors.lastname: Vogt
authors.forename: Friederike
authors.initials: F
authors.lastname: Tewes
authors.forename: Gustavo
authors.initials: G
authors.lastname: Santiso-Quinones
authors.forename: Hansjörg
authors.initials: H
authors.lastname: Grützmacher
mesh_terms: D001372:Aza Compounds / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010084:Oxidation-Reduction; D044367:Phase Transition; D059205:Renewable Energy; D012428:Ruthenium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D001372:Aza Compounds; D009942:Organometallic Compounds; D014867:Water; D002245:Carbon Dioxide; D012428:Ruthenium; D006859:Hydrogen; D000432:Methanol