作者:Masato Nanjo、Takaomi Sasage、Kunio Mochida
DOI:10.1016/s0022-328x(02)02157-5
日期:2003.2
Alkyl(chloro)ethoxygermanes, RGe(OEt)(n)Cl3-n (R = i-Pr, n = 0; R = t-Bu, n = 0-3; R = cyclo-C6H11, n = 0) were hydrolyzed with aqueous NaOH in xylene at 130-140 degreesC to give cage hexakis(alkylgermasesquioxane)s, (RGe)(6)O-9. These structures of cage (RGe)(6)O-9 were fully confirmed by spectroscopic and X-ray diffraction methods. t-Butyldichloro(ethoxy)germane, t-BuGe(OEt)Cl-2, was carefully treated with water at 5 degreesC for 3 h to afford cis, trans-1,3,5-tri-t-butyl-1,3,5-trichlorocyclotrigermoxane, (t-BuClGeO)(3). Hydrolysis of (t-BuClGeO)(3) at 5 degreesC for additional 33 h gave a tricyclic anti-form ladder 5,7-dichloro-1,3,5,7,9,1 1-hexat-butyltricyclo[7.3.1.1(3.7)]hexagermoxanes, (t-BuGe)(6)O8Cl2. The tricyclic ladder (t-BuGe)(6)O8Cl2 was also prepared by hydrolysis of t-butyl(chloro)diethoxygermane, t-BuGe(OEt)(2)Cl, at 5 degreesC for 6 It, and its structure was determined by spectroscopic and X-ray diffraction analysis. The tricyclic ladder germoxane reacted with aqueous NaOH in xylene at 130-140 degreesC for 3 h to afford hexakis(t-butylgermasesquioxane), (t-BuGe)(6)O-9. The formation mechanism of the germasesquioxane, (t-BuGe)(6)O-9 from t-butyl(chloro)ethoxygermanes, t-BuGe(OEt)(n)Cl3-n (n = 0-3) is also discussed. (C) 2002 Elsevier Science B.V. All rights reserved.