Reactivity of a Ruthenium–Carbonyl Complex in the Methanol Dehydrogenation Reaction

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‐Pr(3)) {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 H(2), formate, and carbonate. Dihydrogen is the only gas detected and a turnover frequency up to 55 h(−1) at 82 °C is reached. Complex 2 bears 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‐iPr(3))(2) is occasionally observed, which is also an active methanol dehydrogenation catalyst.