The successful synthesis of sodium triphenylgermanethiol (I), (CsH5)3GeSSa, and disodium diphen5lgermanedithio1, (CsHs)zGe(Sr'Ja)z, have made it possible to carry out reactions with RX type compounds y~elding a variety of organogermanium-sulphur con~pounds. In addition, triphenylgerrnanethiol, (CsH5)3GeSH, has been synthesized for the first time. Reactions of these compounds are related to analogous group IV element compounds. Phqsical and chemical properties of these new compounds are also discussed.Although many organogermanium compounds have been prepared within the last 20 years, only relatively few papers (17 out of about 400) have dealt with thiogermanium compounds. Basically two methods are available for synthesizing tetraalkyl-and tetraaryl-thiogermanes (2-6) :Bis-trialkyl(ary1) sulphides, RgGeSGeR3, have been prepared by Burschkies (7) by the reaction of substituted monobromogermanes with sodium sulphide. Anderson (8, 9) has synthesized a group of triethylgermanethiol derivatives as follows:EtsGeOAc + ArSH Et3GeSAr + HOAc.I t should be noted that this method is limited to those cases where the product acid is the most volatile compound of the reaction mixture.Finally, a few compounds of the types RzGeS (10-15), RzGe(SCN)2 (16), and (R2GeS)zS (17), where R is usually an alkyl substituent, have also been reported.The sparsity of information about this general area of organogermanium chemistry and more specifically about the chemistry of di-and tri-phenylgermanethiol derivatives prompted us to investigate possible methods for preparing these general trpes of cornpounds. RESULTS AND DISCUSSIONGenerally considered, organogermanium and organosilicon compounds exhibit rather similar properties. Considerable difference exists, however, between the hydrolytic stability of germanium-sulphur and silicon-sulphur bonds.Due to the stability of the recently described sodium triphenylgermanethiol, (CGHS)aGeSNa ( I ) , attempts were made t o prepare the analogous compounds of the other group 1V elements. Sodium triphenylsilanethiol, (C8H5)3SiSNar could not be formed under the preparative conditions used (hydrated sodium sulphide) probably due t o 'Presented at the Symposium on Organometallic Cofnpoztnds, Vancouver, British Columbia, September 4-6, 1962, sponsored by

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Salzsaure Lösungen von Germanium(IV)‐chlorid zeigen oberhalb einer Salzsäurekonzentration von 6 n im UV‐Gebiet von 2100–2150 Å eine starke Absorption, die sowohl der Salzsäure‐ als auch Germaniumkonzentration proportional ist. Im untersuchten Germaniumkonzentrationsbereich gilt bei konstanter Säurekonzentration das Lambert‐Beersche Gesetz. Da weder eine wäßrige Lösung von GeO2 noch GeCl4 in Methanol unter vergleichbaren Konzentrationsbedingungen eine nennenswerte Absorption aufweisen, wird als absorbierender Körper in salzsaurer Lösung das GeCl 62−‐Ion angenommen. Aus den Meßergebnissen konnte die Gleichgewichtskonstante der Reaktion 2 Cl− + GeCl4 ⇌ GeCl 62− sowie der molare Extinktionskoeffizient berechnet werden. Alkalichloride erhöhen das Absorptionsvermögen salzsaurer Lösungen von GeCl4. Der Effekt nimmt innerhalb der Gruppe vom LiCl zum CsCl hin ab.