Germanium dichloride

The existence of germanium(II) oxide is well established. It is a solid which can be made, for example, by the action of water on germanium dichloride, GeCl2 ... 

The determination of the structure of the unstable germanium dichloride molecule serves here as an example of the application of the combined experiment. The... 

Fig. iO. The reactor-nozzle-system as applied for the electron diffraction investigation of germanium dichloride ... 

The structure of germanium dichloride is characterized by the following parameters... 

The rate-limiting step is believed to be the surface reaction between adsorbed molecular hydrogen and germanium dichloride (3.111) ... 

Bis(chloromethyl)germanium dichloride, isolation in preparation of (chloromethyl) germanium trichloride, 6 40... 

In the reaction of lithiated 2-hydroxybiphenyl and 2 -hydroxy-m-terphenyl with germanium dichloride-dioxane complex and GeCLj, respectively, spirocyclic ger-mabiphenanthrene compounds (Scheme 4) and l-oxa-10-germaphenanthrene (Scheme 5) were formed11. 

The yellow crystalline half-sandwich 38 was prepared in 81% yield from the tricyclic zirconium species 37 upon treatment with the dioxane complex of germanium dichloride in tetrahydrofuran (THF) at 70 °C for 48 h. lodination of 38 in toluene at —30 °C led to the immediate disappearence of the purple color. After stirring for 18 h at 25 °C the tricyclic cage compound 39 was formed quantitatively according to nuclear magnetic resonance (NMR) spectra. Due to its excellent solubility the isolated yield dropped to only 21% (Scheme 14) <20030M2891>. 

Treatment of trichlorogermylphosphine 183 with a twofold excess of DBU in tetrahydrofuran gave bis[bis(trimethylsilyl)methyl]diphosphene (186), bis(trimethylsilyl)methylphosphine (187), and diphosphine 188 in the proportions 55 25 20. The proposed reaction mechanism is depicted in Scheme 4. Compound 184 was probably first formed through the elimination of germanium dichloride, and then reacted further with an excess of DBU in two competitive reaction routes to give compounds 186-188. Intermolecular dehydrochlorination of 184 afforded diphosphene 186, while intramolecular dehydrochlorination of 184 resulted in 187 and 188 via the triplet phos-phinidene intermediate 185 (84CC1621). 

The reaction of trichlorogermylphosphines (226) with DBU gave chloro-phosphine 227 and a DBU -germanium dichloride complex (228) (84CC1621). 

Germanium Dichloride. Cl2Ge mol wt 143.51. Ge 50.59%, Cl 49.41%, GeCl2. Obtained as residue upon low temp distillation of GeHClj (prepd by the reaction of hydrogen chloride with germanium monosulfide) Moulton, Miller, J. Am. Chem. Soc. 78, 2702 (1956). 

It can also be shown that the reactions of stannic chloride [92] and germanium tetrachloride [93] with potassium give chemiluminescence due to stannous chloride with SnCl and germanium dichloride respectively. The detailed spectroscopic analyses allow a reassessment [94] of the primary chemiluminescence mechanism of Heller and Polanyi... 

Ge(CH2Cl)Cl3 (Chloromethyl)ger-manium trichloride, 6 39 Ge(CH2Cl)2Cl2 Bis(chloromethyl)-germanium dichloride, 6 40 Ge(CH3)l3 Methylgermanium tri-iodide, 3 64, 66... 

Very recently we have found that 43 is easily accessible by a simple one-pot sythesis (Eq. 11). Treatment of the germanium dichloride dioxan complex with the aryl Grignaid reagent in the presence of magnesium furnishes 43 in one step and in an acceptable yield of about 30 % [23]. 

The surface reaction between adsorbed molecular hydrogen and germanium dichloride is believed to be rate-limiting. The reaction follows an elementary rate law with the rate being proportional to the fraction of the surface covered by GeCU times the square of the fraction of the surface covered by molecular hydrogen. 

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