Gallium Hydride‐Catalyzed Selective Hydroboration of Unsaturated Organic Substrates

The first examples of tetrasubstituted conjugated bis-guanidinate (CBG) supported monomeric and thermally stable gallium dihalides [LGaX₂], (X=Cl (Ga-Cl), I (Ga-I)) and dihydride (Ga-H) [LGaH₂] (where L={(ArHN)(ArN)-C=N-C=(NAr)(NHAr)}; Ar=2,6-Et₂-C₆H₃) compounds are reported. The reaction of in situ generated LLi with 1.0 equiv. GaX₃ (X=Cl, I) afforded compounds Ga-Cl and Ga-I. The reaction between Ga-Cl and Li[HBEt₃] in benzene yielded the dihydride compound Ga-H. All reported compounds (Ga-Cl, Ga-I, and Ga-H) were characterized by NMR, HRMS, and single-crystal X-ray diffraction studies. Ga-H was probed for the hydroboration of carbodiimides (CDI), isocyanates, and isothiocyanates with HBpin. Compound Ga-H was also found effective for the catalytic hydroboration of imines, nitriles, alkynes, esters, and formates, affording the corresponding products in quantitative yields. Stoichiometric reactions with a CDI were performed to establish the catalytic cycle.