Germanium preparative methods

A variety of preparation methods are known for transient germanium-chalcogen double bond species some of them seemed to be useful also for the synthesis of kinetically stabilized systems. Indeed, the reaction of a germylene with an appropriate chalcogen source was found to be one of the most versatile and general methods for the synthesis of stable germanium-containing heavy ketones (Scheme 21). 

In conclusion, enantioselective microbial reductions of silicon and germanium compounds containing an El-C(0)Me (El = Si, Ge) moiety El-CH(OH)Me] proved to be an efficient preparative method for the synthesis of optically active silanes, germanes, and digermanes. Furthermore, the commercially available yeast Saccharomyces cerevisiae (DHW S-3) is considered to be an efficient biocatalyst for this particular type of bioconversion. 

The product is a solid yellow hydrated oxide. If prepared by a method in the absence of water, a black anhydrous product is obtained. Germanium(II) oxide is stable in air at room temperature but is readily oxidised when heated in air or when treated at room temperature with, for example, nitric acid, hydrogen peroxide, or potassium manganate(VII). When heated in the absence of air it disproportionates at 800 K ... 

Analysis of refined germanium products is done in a wide variety of ways, including several methods that have become ASTM standards (47). Electronic-grade Ge02 is analyzed using an emission spectrograph to determine its spectrographic purity. Its volatile content is measured in accord with ASTM F5 and its bulk density with F6. Other ASTM standards cover the preparation of a metal biHet from a sample of the oxide (F27), and the determination of the conductivity type (F42) and resistivity (F43) of the biHet. 

The state of the synthetic art in this area, in 1979, is much more satisfactory. During the past decade, several new synthetic developments have occurred such that we are closer to the point where the limitations upon synthesis of trifluoromethyl compounds are related more to stability problems in isolated cases, and are not nearly so much due to lack of widely applicable synthetic techniques. We find ourselves, for example, in a position in 1979 where the germanium compound, Ge(CF3)4, which in the past decade, was considered by many workers to be of insufficient stability to permit isolation, has been prepared by four independent methods and is known to be stable to over 100°C. Many of these new synthetic techniques have emerged from studies conducted in our laboratory at the University of Texas and previously... 

Aminolysis of the corresponding halides is the preferred method for the synthesis of dialkylamino derivatives of boron,1 silicon,2 germanium,3 phosphorus,4 arsenic,5 and sulfur.6 (Dialkylamino) chlorosilanes are prepared stepwise by the reaction of silicon tetrachloride with dialkylamines. This method may be utilized equally well for the conversion of alkyl- or aryl-substituted halides [e.g., (CH3) SiCl4. ] or of oxide and sulfide halides (e.g., POCl3 or PSC13) to the corresponding dialkylamino compounds. 

The introduction of high-resolution, high-efficiency /-ray detectors composed of lithium-drifted germanium crystals has revolutionised /-measurement techniques. Thus, /-spectrometry allows the rapid measurement of relatively low-activity samples without complex analytical preparations. A technique described by Michel et al. [25] uses Ge(Li) /-ray detectors for the simultaneous measurements of 228radium and 226radium in natural waters. This method simplifies the analytical procedures and reduces the labour while improving the precision, accuracy, and detection limits. 

The catenation abihty of lead being considerably lower than that of germanium or tin, plumbanes with Pb—Pb bonds are quite difficult to prepare, even though a number of such compounds have been synthesized. As already pointed out, the main method for the preparation of this type of compound is the reaction of an appropriate Grignard reagent with PbCl2159, e.g. 

Several methods, similar to those used to produce organosilicon compounds, are available for the preparation of germanium organyls. Organogermanium halides, which are the source of practically all other types of germanium organyls, can be formed by the direct reaction of aryl and alkyl halides with Ge/Cu alloys (equation 1). 

The methods for the preparation of compounds containing germanium-nitrogen bonds have been the subject of a recent review.140... 

The digermenes were the first stable doubly bonded germanium species to be prepared,3 5a 7,8 mainly by the routes displayed in Scheme 9. These routes have still been used during the past 4 years, but new ones have also been discovered. Depending on the method used and on the substituents on germanium, stable or transient digermenes have been obtained. 

As the simultaneous creation of Ge = C and P = C double bonds are unlikely, the P = C double bond, much less reactive than the Ge = C double bond, was formed first.173196 was prepared by debromofluorination of 197 [obtained by reaction of ArP = C(Br)Li181 with dimesityldifluorogermane] with ft-butyllithium at low temperature (Scheme 42). The reaction, followed by 31P NMR between -90°C and room temperature, showed the immediate formation of the lithio compound 198, which lost LiF at -60°C to give the germaphosphaallene 196 in 65-70% yield. 196 was stable at -50°C and dimerized slowly above this temperature. It was the first allenic compound of germanium to be characterized by physicochemical methods. 

Despite the fact that germanium is etched at the faster rate for a given set of plasma conditions, it does not become incorporated into the polymer matrix under the conditions of these experiments. This provides a convenient method to prepare films containing no cathode material but are essentially plasma polymerized polytetra-fluoroethylene. The small oxygen signal observed in the ESCA spectrum of this... 

The direct electrochemical synthesis of metal alkoxides by the anodic dissolution of metals into alcohols containing conducting electrolytes was initially demonstrated by Szilard in 1906 for the methoxides of copper and lead.19 More recently the method has received some attention particularly in the patent literature.29-25 The preparation of the ethoxides of silicon, titanium, germanium, zirconium and tantalum by electrolysis of ethanolic solutions of NH Cl has been patented, although the production of the ethoxides was found to cease after several hours.24,25... 

The alkoxides of both oxidation states were obtained by metathesis of germanium halides (chlorides and iodides) with alkali alkoxides [1488, 1142, 857, 1535]. The yields can be increased by application of GeCl4 solvates with Py or NH3 or amines [3, 222] (method 5) and also by alcohol interchange of ethoxides (method 6) or alcoholysis of Ge[Si(NR3)2]2 [568, 1543] (method 4). The application of alkali alkoxides in the preparation of Ge(OR)4is possible in contrast to that of analogous derivatives of Sn(IV) and Zr due presumably to the much lower stability of corresponding alkoxogermanates the intermediate products of the corresponding reactions because of stability — of the tetrahedral coordination for Ge. The direct electrochemical preparation of Ge(OEt)4... 

Parsa [228] has described a sequential radiochemical method for the determination of thorium (and uranium) in soils. Mukhtar et al. [229] have described a laser fluorometric method for the determination of thorium (and uranium) in soils. Steam digestion has been employed in the preparation of soil samples for the determination of thorium (and uranium) [230]. Thorium (and uranium) were determined by X-ray fluorescence using a germanium planar detector and by chemometric techniques. No sample preparation was required in this method [231]. 

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