Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(≡CtBu)(CH₂tBu)₃with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(≡SiOH)(≡SiNH₂)], leads to [(≡SiNH₂−)(≡SiO−)W(≡CHtBu)(CH₂tBu)₂] and [(≡SiNH₂−)(≡SiO−)W(=CHtBu)₂(CH₂tBu). Variable temperature,¹H–¹H 2D double-quantum,¹H–¹³C HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(≡Si−OH)(≡Si−NH₂)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface–complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 °C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.