Compounds with Direct Gallium-Lanthanum and Gallium-Zinc Bonds

The reduction of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1) {dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene} with 2 equiv of sodium in Et2O affords complex (dpp-Bian)Ga-Na(Et2O)(3) (2), containing a gallium-sodium direct bond. The gallium-zinc complex with a chiral amido-imino ligand, (dpp-Bian)Ga-Zn{dpp-Bian(Bu-n)} (4), has been prepared by the salt elimination reaction between 2 and [{dpp-Bian(Bu-n)}ZnCl](2) (3). Reduction of complex (dpp-Bian)Ga-Zn(dpp-Bian) (5) with 1 equiv of potassium gave the gallium-zinc complex [(dpp-Bian)Ga-Zn(dpp-Bian)]-[K(thf)(5.5)] (6). Lanthanum dicyclopentadienides [(C5Me4Et)(2)LaCl2]-[K(thf)(2)] (7) and [(C5Me5)(2)LaCl2][Na(Et2O)(2)] (8) react with 2 to give the first complexes with gallium-lanthanum bonds, (dpp-Bian)Ga-La(C5Me4Et)(2)(thf) (9) and (dpp-Bian)Ga-La(C5Me5)(2)(thf) (10), respectively. The newly prepared complexes 4, 6, 9, and 10 have been characterized by H-1 nuclear magnetic resonance and infrared spectroscopy; the molecular structures of 4, 6, and 9 have been determined by single-crystal X-ray analysis. The electronic structures of 4 and 10 have been examined by density functional theory calculations.