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Compounds with Direct Gallium–Lanthanum and Gallium–Zinc Bonds

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posted on 11.07.2011, 00:00 by Igor L. Fedushkin, Anton N. Lukoyanov, Alexandra N. Tishkina, Maxim O. Maslov, Sergey Yu. Ketkov, Markus Hummert
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(nBu)} (4), has been prepared by the salt elimination reaction between 2 and [{dpp-Bian(nBu)}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)2LaCl2][K(thf)2] (7) and [(C5Me5)2LaCl2][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 1H 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.