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The pioneers of organogermanium chemistry, Morgan and Drew149 , were the ﬁrst to synthesize polyorganylgermoxanol and polyorganylgermsesquioxane, which for a long time were termed organyl germanoic acid and its anhydride, respectively. 5 , depending on the reaction conditions. The authors were sure that the product had a structure intermediate between those of phenylgermanoic acid PhGeOOH and its anhydride (PhGeO)2 O. e. 5 )n , by treatment of PhGeCl3 with a dilute aqueous ammonia solution. The anhydride had high solubility in alkalis and could be reprecipitated from the alkali solution by carbon dioxide.
The same types of compounds were synthesized by reaction of Me3 GeCl with the silver salts of the corresponding acids410,412,413 . Similarly, Srivastava and Tandon prepared (Ph3 GeO)2 Y with Y D SO2 and SeO2 415 . In 1961–1964 Schmidbaur, Schmidt and coworkers405,416 , synthesized a series of compounds R4 n Ge(OSiR03 )n with R, R0 D Me, Et; n D 1–3. For example, trimethyl(trimethylsiloxy)germane Me3 GeOSiMe3 and dimethylbis(trimethylsiloxy)germane Me2 Ge(OSiMe3 )2 were obtained by the reaction of alkali metal trimethylsilanolates Me3 SiOM and Me3 GeCl or Me2 GeCl2 .
In 1954, Brook and Gilman195 pointed out that one of the ﬁrst arylalkoxygermanes Ph3 GeOMe was the thermal decomposition product of Ph3 GeCOOMe at 250 ° C with CO elimination. For comparison, triphenylmethoxygermane was synthesized from Ph3 GeBr and MeONa. In 1968, Peddle and Ward390 discovered the rearrangement of Ph3 GeCH2 OH to Ph3 GeOMe. In 1961, Grifﬁths and Onyszchuk373 found that the reaction of MeGeH2 Br and MeONa at 80 ° C gave MeGeH2 OMe, which slowly decomposed to form the polymer (MeGeH)n and MeOH.