DFT Provides Insight into the Additive-Free Conversion of Aqueous Methanol to Dihydrogen Catalyzed by [Ru(trop2 dad)]: Importance of the (Electronic) Flexibility of the Diazadiene Moiety

Journal of the American Chemical Society
Vivek SinhaBas de Bruin

Abstract

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...Continue Reading

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