Carberry et al.

, p. 839 (1975)

Tetramethylsilane in synthesis: Selective mono- and polymethylations of germanium tetrachloride

Bordeau, Michel,Djamei, S. Mohammad,Dunoguès, Jacques

, p. 1087 - 1089 (1985)

In the presence of catalytic amounts of aluminum bromide (or chloride), selective mono-, di-, tri-, or tetramethylation of germanium tetrachloride was effected in high yield with tetramethylsilane (Me4Si) as the methylating reagent. According to the Me4Si/GeCl4 ratio, MeGeCl3, Me2GeCl2, Me3GeCl, and Me4Ge were prepared in 66, 86, 100, and 91% maximum yields, respectively. In these reactions, Me4Si was converted into Me3SiCl and subsequently Me2SiCl2. A mechanism for methylation is proposed, involving the initial formation of Me4Ge (observed regardless of the proportions of starting reagents) followed by disproportionation reactions, with methylchlorosilanes or -germanes present when the initial molecular ratio Me4Si/GeCl4 was lower than 4/1.

Dolgoplosk et al.

, p. 339,340,344 (1977)

Van de Vondel

, p. 400,401 (1965)

Mechanism and Selectivity of Aryltrimethylgermane Cation Radical Fragmentations

Feinberg, Elizabeth C.,Dinnocenzo, Joseph P.

supporting information, p. 8639 - 8644 (2020/07/03)

Aryltrimethylgermane cation radicals were generated by nanosecond transient absorption spectroscopy. Transient kinetics experiments show that the aryltrimethylgermane cation radicals react with added nucleophiles in reactions that are first-order in both

Trichlorosilylation of chlorogermanes and chlorostannanes with HSiCl3/Net3 followed by base-catalysed formation of (Me3Ge)2Si(SiCl3)2 and related branched stannylsilanes

Mueller, Lars,Du Mont, Wolf-Walther,Ruthe, Frank,Jones, Peter G.,Marsmann, Heinrich C.

, p. 156 - 163 (2007/10/03)

Chlorotrimethylgermane 1 and dichlorodimethylgermane 4 react with trichlorosilane and triethylamine to provide trichlorosilylgermanes Me4-nGe(SiCl3)n (n = 1: 2; n = 2: 5) in fair yields, as distillable liquids. The formation of 2 is followed by base-catalysed decomposition reactions leading to novel solid (Me3Ge)2Si(SiCl3)2 3. Chlorotrialkylstannanes 6a-c (6a: R = CH3, 6b: R = C2H5, 6c: R = n-C4H9) react with trichlorosilane and triethylamine providing the branched silylstannanes (R3Sn)2Si(SiCl3)2 7a-c and traces of silylstannanes R3SnSiCl3 8a-c. Only 7a was isolated in a pure state. Heating 7a or crude 7b and 7c with benzyl chloride leads to the formation of benzyltrichlorosilane (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.

Thermal decomposition of platinum(IV)-silicon, -germanium, and -tin complexes

Levy, Christopher J.,Puddephatt, Richard J.

, p. 4115 - 4120 (2008/10/08)

The thermal decomposition of a number of complexes of the type [PtMe2(Me3E)X(diimine)] (E = Si, Ge, Sn; X = Cl, Br, I) has been studied. The thermal stability of complexes, as determined by thermogravimetric analysis (TGA), varies depending on the diimine ligand in the order 2,2′-bipyridyl (bpy) > 4,4′-di-tert-butyl-2,2′-bipyridyl (bpy-tbu2) > N-(2-(dimethylamino)ethyl)pyridine-2-aldimine (paen-me2) > (2-imino-n-propyl)pyridine (py-n-pr). Stability also varies according to the trends E = Sn ≈ Ge > Si and X = I > Br > Cl. The products of thermal decomposition have also been determined by 1H NMR and three distinct modes of decomposition are evident: reductive elimination of Me3EX, reductive elimination of Me4E, and α-elimination of Me2E. The competition between reductive elimination of Me3EX and Me4E depends primarily on the halide, X, with the ratio Me3EX:Me4E highest for X = Cl and lowest for X = I. The competition between reductive elimination and α-elimination depends primarily on E, with the tendency to α-elimination of Me2E increasing as E = Si 2(Me3Si)(bpy)] as 233 ± 14 kJ mol-1.