Silica Supported Organometallic Ir^I Complexes Enable Efficient Catalytic Methane Borylation

Catalytic C–H borylation is an attractive method for the conversion of the most abundant hydrocarbon, methane (CH₄), to a mild nucleophilic building block. However, existing CH₄ borylation catalysts often suffer from low turnover numbers and conversions, which is hypothesized to result from inactive metal hydride agglomerates. Herein we report that the heterogenization of a bisphosphine molecular precatalyst, [(dmpe)­Ir­(cod)­CH₃], onto amorphous silica dramatically enhances its performance, yielding a catalyst that is 12-times more efficient than the current standard for CH₄ borylation. The catalyst affords over 2000 turnovers at 150 °C in 16 h with a selectivity of 91.5% for mono- vs diborylation. Higher catalyst loadings improve yield and selectivity for the monoborylated product (H₃CBpin) with 82.8% yield and >99% selectivity being achieved with 1255 turnovers. X-ray absorption and dynamic nuclear polarization-enhanced solid-state NMR spectroscopic studies identify the supported precatalyst as an Ir^I species, and indicate that upon completion of catalysis, multinuclear Ir polyhydrides are not formed. This is consistent with the hypothesis that immobilization of the organometallic Ir species on a surface prevents bimolecular decomposition pathways. Immobilization of the homogeneous Ir^I fragment onto amorphous silica represents a unique and simple strategy to improve the TON and longevity of a CH₄ borylation catalyst.