DFT Provides Insight into the Additive-Free Conversion of Aqueous Methanol to Dihydrogen Catalyzed by [Ru(trop2dad)]: Importance of the (Electronic) Flexibility of the Diazadiene Moiety.

The mechanism for complete dehydrogenation of aqueous methanol to CO2 and three equivalents of H2 catalyzed by [Ru(trop2dad)] was investigated with DFT (trop2dad = 1,4-bis(5 H-dibenzo[ a, d]cyclohepten-5-yl)-1,4-diazabuta-1,3-diene). To date, this is the only catalyst that promotes the acceptorless dehydrogenation of aqueous methanol in homogeneous phase under mild conditions without the addition of an additive (base, acid, or a secondary catalyst). A detailed understanding of the mechanism of this transformation may therefore be of significant importance for the conversion of liquid organic fuels. Previous computational studies using simplified models of the catalyst suggested entirely ligand-centered reaction pathways with rather high-energy barriers for complete dehydrogenation of aqueous methanol. These are, however, not consistent with the experimental data. In the present paper, we reveal a different reaction mechanism for aqueous methanol dehydrogenation that involves metal-ligand cooperativity involving the diazadiene (dad) ligand and has substantially lower barriers, in good agreement with the experimental data. The dad moiety of the ligand actively participates in the alcohol activation mechanism. In the first step of the reaction, the dad ligand rearranges from a σ- to a π-bound coordination mode. This adjusts the electronic structure of both the metal and the ligand, leading to an enhanced Brønsted basicity of the nitrogen centers and higher Lewis acidity of the ruthenium center. As a result, concerted proton-hydride transfer to/from metal-hydride and N-protonated dad-ligand moieties becomes possible, leading to low-barrier metal-ligand cooperative elementary steps for alcohol activation and H2 elimination.