Examples of compounds with gallium–boron donor–acceptor bonds, HC[MeC(2,6-Pri2C6H3)N]2Ga→B(C6F5)33 and (η5-C5Me5)Ga→B(C6F5)34 have been prepared by treatment of the free gallanediyls with B(C6F5)3; the structures of both compounds were determined by X-ray crystallography.