Mechanistic Insights into Alkane Metathesis Catalyzed by Silica-Supported Tantalum Hydrides: A DFT Study

Alkane metathesis transforms small alkanes into their higher and lower homologues. The reaction is catalyzed by either supported d⁰ metal hydrides (M = Ta, W) or d⁰ alkyl alkylidene complexes (M = Ta, Mo, W, Re). For the silica-supported tantalum hydrides, several reaction mechanisms have been proposed. We performed DFT-D3 calculations to analyze the viability of the proposed pathways and compare them with alkane hydrogenolysis, which is a competitive process observed at the early stages of the reaction. The results show that the reaction mechanisms for alkane metathesis and for alkane hydrogenolysis present similar energetics, and this is consistent with the fact that the process taking place depends on the concentrations of the initial reactants. Overall, a modified version of the so-called one-site mechanism that involves alkyl alkylidene intermediates appears to be more likely and consistent with experiments. According to this proposal, tantalum hydrides are precursors of the alkyl alkylidene active species. During precursor activation, H₂ is released and this allows alkane hydrogenolysis to occur. In contrast, the catalytic cycle implies only the reaction with alkane molecules in excess and does not form H₂. Thus, the activity for alkane hydrogenolysis decreases. The catalytic cycle proposed here implies three stages: (i) β-H elimination from the alkyl ligand, liberating ethene, (ii) alkene cross-metathesis, allowing olefin substituent exchange, and (iii) formation of the final products and alkyl alkylidene regeneration by olefin insertion and three successive 1,2-CH insertions to the alkylidene followed by α abstraction. These results relate the reactivity of silica-supported hydrides with that of the alkyl alkylidene complexes, the other common catalyst for alkane metathesis.