title: Reactivity of a Ruthenium-Carbonyl Complex in the Methanol Dehydrogenation Reaction.
abstract: Finding new catalysts for the release of molecular hydrogen from methanol is of high relevance in the context of the development of sustainable energy carriers. Herein, we report that the ruthenium complex Ru(salbinapht)(CO)(Pi-Pr3) {salbinapht=2-[({2'-[(2-hydroxybenzyl)amino]-[1,1'-binaphthalen]-2-yl}imino)methyl]phenolato} (2) catalyzes the methanol dehydrogenation reaction in the presence of base and water to yield H2, formate, and carbonate. Dihydrogen is the only gas detected and a turnover frequency up to 55 h-1at 82 °C is reached. Complex2bears a carbonyl ligand that is derived from methanol, as is demonstrated by labeling experiments. The carbonyl ligand can be treated with base to form formate (HCOO-) and hydrogen. The nature of the active species is further shown not to contain a CO ligand but likely still possesses a salen-derived ligand. During catalysis, formation of Ru(CO)2(H)2(P-iPr3)2is occasionally observed, which is also an active methanol dehydrogenation catalyst.
authors.affiliation: Homogeneous, Supramolecular and Bio-Inspired Catalysis Van't Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands.
authors.forename: Fenna F
authors.initials: FF
authors.lastname: van de Watering
authors.affiliation: Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research Faculty of Science Utrecht University Padualaan 8 3584 CH Utrecht The Netherlands.
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.affiliation: Homogeneous, Supramolecular and Bio-Inspired Catalysis Van't Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands.
authors.forename: Wojciech I
authors.initials: WI
authors.lastname: Dzik
authors.affiliation: Homogeneous, Supramolecular and Bio-Inspired Catalysis Van't Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands.
authors.forename: Bas
authors.initials: B
authors.lastname: de Bruin
authors.affiliation: Homogeneous, Supramolecular and Bio-Inspired Catalysis Van't Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands.
authors.forename: Joost N H
authors.identifier: 0000-0001-5024-508X
authors.initials: JN
authors.lastname: Reek
keywords: dehydrogenation; homogeneous catalysis; hydrogen; ruthenium; salen ligands