Aluminum-Hydride-Catalyzed Hydroboration of Carbon Dioxide

This study describes the first use of a bis(phosphoranyl)methanido aluminum hydride, [ClC(PPh₂NMes)₂AlH₂] (2, Mes = Me₃C₆H₂), for the catalytic hydroboration of CO₂. Complex 2 was synthesized by the reaction of a lithium carbenoid [Li(Cl)C(PPh₂NMes)₂] with 2 equiv of AlH₃·NEtMe₂ in toluene at -78 °C. 2 (10 mol %) was able to catalyze the reduction of CO₂ with HBpin in C₆D₆ at 110 °C for 2 days to afford a mixture of methoxyborane [MeOBpin] (3a; yield: 78%, TOF: 0.16 h^-1) and bis(boryl)oxide [pinBOBpin] (3b). When more potent [BH₃·SMe₂] was used instead of HBpin, the catalytic reaction was extremely pure, resulting in the formation of trimethyl borate [B(OMe)₃] (3e) [catalytic loading: 1 mol % (10 mol %); reaction time: 60 min (5 min); yield: 97.6% (>99%); TOF: 292.8 h^-1 (356.4 h^-1)] and B₂O₃ (3f). Mechanistic studies show that the Al-H bond in complex 2 activated CO₂ to form [ClC(PPh₂NMes)₂Al(H){OC(O)H}] (4), which was subsequently reacted with BH₃·SMe₂ to form 3e and 3f, along with the regeneration of complex 2. Complex 2 also shows good catalytic activity toward the hydroboration of carbonyl, nitrile, and alkyne derivatives.