Group 4 Metallocenes Supported on Sulfated Zirconium Oxide Catalyze Benzene C–H Borylation

C-H bond functionalization of arenes with boranes continues to be a challenge in catalysis, with late transition and rare earth metals shown to be catalytically active. In this study, group 4 metallocenes grafted onto acidic sulfated zirconia (SZO) are demonstrated to catalyze arene borylation with pinacolborane (HBpin). Catalysis studies at partial HBpin conversions (59-68%) using Cp₂M(Me)/SZO (M = Ti, Zr, or Hf; Cp = cyclopentadienyl) catalysts reveal that Zr exhibits greater selectivity and activity than Ti and Hf. At 0.16 mol % of Zr, Cp₂ZrMe/SZO achieves 332 turnovers at high HBpin conversion (86%), making this catalyst comparably active to previously reported Ir and Rh C-H borylation catalysts. At 160 °C, a maximum chemoselectivity of 82% for PhBpin was observed at 24% HBpin conversion. The superior activity of ionic Cp₂ZrMe/SZO compared to neutral Cp₂ZrMe/SiO₂ demonstrates the borylation mechanism relies on the highly electrophilic, coordinatively unsaturated cationic sites stabilized by the weakly coordinating sulfated support. Furthermore, both catalysts significantly outperform their molecular analogues, Cp₂ZrMe₂ and [Cp₂ZrMe][B(C₆F₅)₄], suggesting that the support enhances catalytic performance by stabilizing the active species.