Trichlorosilylation of chlorogermanes and chlorostannanes with HSiCl3/Net(3) followed by base-catalysed formation of (Me3Ge)(2)Si(SiCl3)(2) and related branched stannylsilanes

Chlorotrimethylgermane 1 and dichlorodimethylgermane 4 react with trichloro silane and triethylamine to provide trichlorosilylgermanes Me4-nGe(SiCl3)(n ) (n= 1: 2; n=2: 5) in fair yields, as distillable liquids. The formation o f 2 is followed by base-catalysed decomposition reactions leading to novel solid (Me3Ge)(2)Si(SiCl3)(2) 3. Chlorotrialkylstannanes 6a-c (6a: R = CH3, 6b: R=C2H5, 6c: R = n-C4H9) react with trichlorosilane and triethylamine pr oviding the branched silylstannanes (R3Sn)(2)Si(SiCl3)(2) 7a-c and traces o f silylstannanes R3SnSiCl3 8a-c. Only 7a was isolated in a pure state. Heat ing 7a or crude 7b and 7c with benzyl chloride leads to the formation of be nzyltrichlorosilane (10). The constitution of compounds 2, 3, 5 and 7a was confirmed by MS, NMR and analytical data. The structures of C6D6-solvated 3 and C6H6-solvated 7a were determined by X-ray diffraction, and shown to be isotypic. (C) 1999 Elsevier Science S.A. All rights reserved.