G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, Russia.
Chemistry. 2010 Jul 5;16(25):7563-71. doi: 10.1002/chem.201000377.
The reduction of digallane [(dpp-bian)Ga-Ga(dpp-bian)] (1) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with lithium and sodium in diethyl ether, or with potassium in THF affords compounds featuring the direct alkali metal-gallium bonds, [(dpp-bian)Ga-Li(Et(2)O)(3)] (2), [(dpp-bian)Ga-Na(Et(2)O)(3)] (3), and [(dpp-bian)Ga-K(thf)(5)] (7), respectively. Crystallization of 3 from DME produces compound [(dpp-bian)Ga-Na(dme)(2)] (4). Dissolution of 3 in THF and subsequent crystallization from diethyl ether gives [(dpp-bian)Ga-Na(thf)(3)(Et(2)O)] (5). Ionic (dpp-bian)GaNa([18]crown-6)(thf)(2) (6a) and (dpp-bian)GaNa(Ph(3)PO)(3)(thf) (6b) were obtained from THF after treatment of 3 with [18]crown-6 and Ph(3)PO, respectively. The reduction of 1 with Group 2 metals in THF affords (dpp-bian)GaM(thf)(n) (M=Mg (8), n=3; M=Ca (9), Sr (10), n=4; M=Ba (11), n=5). The molecular structures of 4-7 and 11 have been determined by X-ray crystallography. The Ga-Na bond lengths in 3-5 vary notably depending on the coordination environment of the sodium atom.
化合物 1（dpp-bian=1,2-双[(2,6-二异丙基苯基)亚氨基]蒽）与锂和钠在乙醚中，或与钾在四氢呋喃中反应，生成含有直接碱金属-镓键的化合物，分别为[(dpp-bian)Ga-Li(Et(2)O)(3)] (2)、[(dpp-bian)Ga-Na(Et(2)O)(3)] (3)和[(dpp-bian)Ga-K(thf)(5)] (7)。3 从 DME 结晶得到化合物 [(dpp-bian)Ga-Na(dme)(2)] (4)。将 3 溶解在 THF 中，然后从乙醚中结晶得到[(dpp-bian)Ga-Na(thf)(3)(Et(2)O)] (5)。将 3 溶解在 THF 中，然后从乙醚中结晶得到[(dpp-bian)Ga-Na(thf)(3)(Et(2)O)] (5)。用 18-冠-6 和 Ph(3)PO 处理 3 后，可分别从 THF 中得到离子(dpp-bian)GaNa([18]冠-6)(thf)(2) (6a)和(dpp-bian)GaNa(Ph(3)PO)(3)(thf) (6b)。在 THF 中用第 2 族金属还原 1，得到(dpp-bian)GaM(thf)(n) (M=Mg (8)，n=3；M=Ca (9)，Sr (10)，n=4；M=Ba (11)，n=5)。通过 X 射线晶体学确定了 4-7 和 11 的分子结构。3-5 中 Ga-Na 键长随钠原子的配位环境显著变化。
