Digermyl sulfide

Digermyl sulfide (digermathiane) has been prepared by the reaction of iodoger-mane with mercury(II) sulfide and, more recently, from bromogermane and dilithium sulfide in dimethyl ether. (Methylthio)germane has been prepared by... 

The trap at -78° contains pure digermyl sulfide [(GeH3)2S 0.0404 g, 0.22 mmole identified by its H NMR, infrared, and Raman spectra ]. Excess hydrogen sulfide, identified by infrared spectroscopy, collects in the trap at -196°, while a small amount of nonvolatile white material remains in the flask. The yield of digermyl sulfide, based on the carbodiimide, is 92%. 

Digermyl sulfide is a colorless liquid that has a vapor pressure of 5 torr at 0°. It is relatively stable at room temperature when sealed in a Pyrex glass tube, but it is recommended that it be kept at -196°. Its vapor pressure permits easy handling under vacuum conditions. It has a very distinct foul odor and should be kept in (or close to) a hood at all times. 

Digermyl sulfide has been used as an intermediate in the preparation of germanethiol (mercaptogermane),2 4 and digermyl ether.5 In view of the utility of disilyl sulfide as an intermediate,6 it seems likely that the germyl analog will be exploited further. 

Caution. The toxicity of digermyl sulfide is unknown. It should be handled in an efficient fume hood. 

After 6 hours the vessel is opened to the vacuum system and the contents are fractionated using traps maintained at — 23° (carbon tetrachloride slush), — 64°, and — 96°. The second trap retains digermyl sulfide (ca. 2.3 mmoles, 80% yield based on lithium). The separation of the product from bromogermane can be accomplished by distillation in a low-temperature column.7... 

The purity of the product is best checked by its infrared spectrum (2090, 2065, 931, 849, 819, 577, 556, 412 cm.-1). Bromogermane has prominent bands at 2110, 870, 830, and 580 cm.-1, and considerable rotation fine structure is visible on most of these. No such detail is visible on any of the bands in the spectrum of digermyl sulfide. 

Digermyl sulfide is a colorless liquid with a vapor pressure of 1 mm. at 0°, and an intense, nauseating odor. It is stable for short periods at room temperature in the absence of air and moisture but is best stored in sealed ampuls at liquid-nitrogen temperature. The n.m.r. spectrum has a single line at i4.64. 

---