Hydroboration and Deoxygenation of CO₂ Mediated by a Gallium(I) Cation

Hydroboration of CO₂ to formoxy borane occurs under ambient conditions in acetonitrile using pinacolborane HBpin in the presence of gallium(I) cation [(Me₄TACD)Ga][BAr₄] (1; Me₄TACD = N,N',N″,N'''-tetramethyl-1,4,7,10-tetraazacyclododecane; Ar = C₆H₃-3,5-Me₂). Slow turnover was accompanied by side reactions including ligand scrambling of HBpin to give BH₃(CH₃CN) and crystalline B₂pin₃. When 1 was reacted with CO₂ alone, the formation of the gallium(III) carbonato complex [(Me₄TACD)Ga(κ₂-O₂CO)][BAr₄] (3) along with CO was observed. This complex was assumed to form via the unstable oxido cation [(Me₄TACD)Ga=O]⁺ (4). Reaction of 1 with N₂O in the presence of BPh₃ confirmed the formation of the oxido cation, which was spectroscopically characterized as a triphenylborane adduct [(Me₄TACD)Ga=O(BPh₃)][BAr₄] (4·BPh). CO was also detected when CO₂ was reacted with 1 in the presence of HBpin, suggesting that compound 3 may also be formed in initial stages of catalysis. Compound 3 reacts with HBpin to give formoxy borane, borane redistribution products, and an unidentified Me₄TACD-containing species 5, which was also observed in "catalytic" runs starting from 1, HBpin, and CO₂. Hydroboration of CO₂ using HBpin with slow turnover and competitive ligand scrambling was also observed in the presence of gallium(III) hydride dication [(Me₄TACD)GaH][BAr₄]₂ (2), which is unreactive toward CO₂ in the absence of HBpin.