Reduction of digallane (dpp-bian)Ga—Ga(dpp-bian) (1) (dpp-bian is the 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene dianion) with metallic sodium in THF leads to the formation of gallylsodium (dpp-bian)Ga—Na(thf)4 (2). Reduction of digallane 1 with dicyclopentadienyltetracarbonyldiiron, vanadocene, and nickelocene furnishes the corresponding gallyl complexes (dpp-bian)Ga—FeCp(CO)2 (3), (dpp-bian)Ga—VCp2 (4) and [(dpp-bian)Ga]2NiCp (5). The reaction of 1 with Cp2Mn gives a gallium-free complex (dpp-bian)MnCp(dme) (6). Carbonylates [{(dpp-bian)Ga—M(CO)5}{Na(thf)2}]2 (M = Cr (7), W (8)) and [{(dppbian)Ga}2FeCp(CO)][Na(dme)3] (9) were obtained by the reaction of carbonyls Cr(CO)6, W(CO)6, and [CpFe(CO)2]2 with compound 2. Diamagnetic derivatives 3, 7, 8, and 9 were characterized by 1H NMR spectra. The structures of products 3—9 were established by single crystal X-ray diffraction.