C−Br Bond Activation of Bromoalkanes with Gallanediyl LGa

Monovalent group 13 diyls are promising reagents for C−X bond activation. We here report on C−Br bond activation reactions of gallanediyl LGa (L=HC[C(Me)NAr)] 2 , Ar=2,6‐ i ‐Pr 2 C 6 H 3 )) with a variety of bromoalkanes. Reactions with alkylbromides R−Br gave the corresponding LGa(Br)R (R=Et 1 , n ‐Pr 2 , i ‐Pr 3 ), while the reaction with dibromomethane in 2 : 1 molar ratio occurred with geminal C−Br bond addition and formation of [LGa(Br)] 2 CH 2 ( 4 ). In contrast, equimolar reaction of LGa with CHBr 3 yielded LGa(Br)CHBr 2 ( 5 ), which reacted with another equiv. of LGa with decomposition and formation of LGaBr 2 . Compounds 1 – 5 were characterized by heteronuclear ( 1 H, 13 C) NMR and IR spectroscopy, as well as single‐crystal X‐ray diffraction (sc‐XRD).